Process for preparing catalysts and catalyst compositions

ABSTRACT

Disclosed are support-activators and catalyst compositions comprising the support-activators for polymerizing olefins in which the support-activator includes clay heteroadduct, prepare from a colloidal phyllosilicate such as a colloidal smectite clay, which is chemically-modified with a heterocoagulation agent. By limiting the amount of heterocoagulation reagent relative to the colloidal smectite clay as described herein, the smectite heteroadduct support-activator is a porous and amorphous solid which can be readily isolated from the resulting slurry by a conventional filtration process, and which can activate metallocenes and related catalysts toward olefin polymerization. Related compositions and processes are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority to U.S. patentapplication Ser. No. 16/773,489, filed Jan. 27, 2020, which isincorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE DISCLOSURE

This disclosure relates to catalyst compositions includingsupport-activators for producing polyethylene and processes forpreparing and using the same.

BACKGROUND OF THE DISCLOSURE

Compounds such as methylaluminoxane (MAO) and arylboranes are commonlyemployed as metallocene catalyst activators or co-catalysts for thepolymerization of olefins. Industrial-scale manufacture of polyolefinresins can employ gas phase or slurry reactor platforms rather thansolution phase conditions, therefore heterogeneous catalyst systems areused for these polymerization systems. The preparation and use of theseheterogeneous polymerization catalysts can be complicated and expensive.For example, when treating an inorganic metal oxide support such assilica or alumina with a catalyst, further use of co-catalysts oractivators such as MAO and arylboranes are often required, which can betime-intensive and expensive. The synthesis of MAO and arylboranesthemselves is atom inefficient, requiring multiple steps and inertconditions, which can increase the costs of using such activators.

Various support-activators have been investigated to attempt to reducethe high costs of aluminoxanes, arylboranes, and other costly activatorsor co-catalysts. For example, U.S. Pat. Nos. 6,107,230 and 9,670,296 toMcDaniel et al. address utilizing derivatives of amorphous alumina andsilica-alumina as both support and co-catalyst for providing metallocenepolymerization activity. U.S. Pat. Nos. 6,632,894 and 7,041,753 also toMcDaniel et al. describe the use of clay minerals in a sol-gel matrix,which can serve as a support-activator for metallocenes, but whichthemselves can be costly to manufacture. Other approaches are seen inthe use of chemically-modified clay minerals, such as seen in the workof Suga et al. in U.S. Pat. No. 5,973,084, Nikano et al. in U.S. Pat.No. 6,531,552, Murase et al. in U.S. Pat. No. 9,751,961, and McCauley inU.S. Pat. No. 5,202,295. These approaches includes process limitationssuch as low catalyst recovery yield, an excessive number of preparativesteps, difficulty in separating the modified clay mineral, or narrowpreparation conditions under which the clay can be successfully modifiedand isolated.

Therefore, there remains a need to improve the ease and economy ofpreparing support-activators. This need is evident whenchemically-modified clay support-activators of sufficient activity aredesired for producing metallocene-based polyolefins, such as highclarity film resins. It would be desirable to develop clay-basedsupport-activators which eliminate the need for aluminoxanes and othercostly activators, which are convenient and economical to prepare andrecover in high yield, and/or which exhibit relatively high activitywith polymerization catalysts such as metallocene compounds.

SUMMARY OF THE DISCLOSURE

Aspects of this disclosure provide new support-activators and processesfor their preparation, new catalyst compositions comprising thesupport-activators, methods for making the catalyst compositions, andprocesses for polymerizing olefins. In an aspect, thechemically-modified clay support-activators can readily activatemetallocene compounds toward polymerization of olefins, and they aresurprisingly easy and cost-effective to prepare and recover in highyield. In particular, the processes and the support-activators of thisdisclosure can largely avoid the previous difficulties in isolatingchemically-modified clay support-activators, for example, from clayparticle digestion and leaching of the octahedral alumina layer of theclay into solution during the activation process, which makes standardfiltration extremely difficult as the clay particles decrease in size.

It has been unexpectedly discovered that when a colloidal smectite clay,such as a dioctahedral smectite clay, is contacted in a liquid carrier(also termed a “diluent”) with a heterocoagulation reagent comprising atleast one cationic polymetallate, and when the heterocoagulation reagentis used in an amount relative to the colloidal smectite clay within aspecific range, a support-activator comprising an isolated smectiteheteroadduct can be synthesized. By limiting the amount ofheterocoagulation reagent relative to the colloidal smectite clay asdescribed herein, the smectite heteroadduct, also termed aheterocoagulated smectite, can be easily isolated from the resultingslurry by a conventional filtration process. The isolation process hasoften been difficult with previous chemically-modified claysupport-activators, where filtration may require days, or multiplewashing and centrifugation steps may be required. Moreover, the smectiteheteroadduct support-activator isolated in accordance with thisdisclosure can be used with few or no washing steps, further enhancingthe usefulness, ease, and economy of preparation and use.

The smectite heteroadducts prepared in this manner, which can be used incombination with co-catalysts such as alkyl aluminum compound, affordvery active support-activators for metallocene olefin polymerizations,particularly when compared to traditional MAO-SiO₂ or borane-derivedsupport-activators. The heterocoagulation agents used in this processcan be very inexpensive and can be used with co-catalysts such as alkylaluminum compounds, which can also be very inexpensive as compared toaluminoxane and borane-based activators.

Furthermore, the isolation of the smectite heteroadducts can be effectedusing a conventional filtration, without the need for centrifugation orhigh dilution of reaction mixtures, and without extensive washing of thesolid thus obtained. This process provides the solid clay heteroadductexhibiting better activity than the corresponding untreated clay, andcomparable or better activity than the more difficult-to-preparepillared clay supports, thereby fulfilling a need.

Moreover, unlike the pillared clays, the heterocoagulated clay materialsof this disclosure are amorphous solids. The preparation of theheterocoagulated clay provides a three-dimensional structure, but onewhich is a non-pillared and non-crystalline and amorphous. While notintending to be bound by theory, it is believed that the regularcrystalline structure of the starting smectite is not simply expandedupon contact with the cationic polymetallates, but rather disrupted uponpreparation of the clay heteroadducts, to provide a non-crystalline,non-layered amorphous material.

Accordingly, in one aspect, this disclosure provides a support-activatorcomprising an isolated smectite heteroadduct, the smectite heteroadductcomprising the contact product in a liquid carrier of [1] a colloidalsmectite clay and [2] a heterocoagulation reagent comprising at leastone cationic polymetallate and in an amount sufficient to provide aslurry of the smectite heteroadduct having a zeta potential in a rangeof from about positive 25 mV (+25 millivolts) to about negative 25 mV(−25 millivolts).

This disclosure also provides, in another aspect, a method of making asupport-activator comprising a smectite heteroadduct, the methodcomprising:

-   -   a) providing a colloidal smectite clay;    -   b) contacting in a liquid carrier the colloidal smectite clay        with a heterocoagulation reagent comprising at least one        cationic polymetallate and in an amount sufficient to provide a        slurry of a smectite heteroadduct having a zeta potential in a        range of from about positive 25 mV (millivolts) to about        negative 25 mV; and    -   c) isolating the smectite heteroadduct from the slurry.

According to a further aspect, this disclosure provides a catalystcomposition for olefin polymerization, the catalyst compositioncomprising:

-   -   a) at least one metallocene compound;    -   b) optionally, at least one co-catalyst; and    -   c) at least one support-activator comprising a calcined smectite        heteroadduct, the smectite heteroadduct comprising the contact        product of [1] a colloidal smectite clay and [2] a        heterocoagulation reagent comprising at least one cationic        polymetallate in a liquid carrier and in an amount sufficient to        provide a slurry of the smectite heteroadduct having a zeta        potential in a range of from about positive 25 mV (millivolts)        to about negative 25 mV.

This disclosure also provides, in another aspect, a method of making anolefin polymerization catalyst, the method comprising contacting in anyorder:

-   -   a) at least one metallocene compound;    -   b) optionally, at least one co-catalyst; and    -   c) at least one support-activator comprising a calcined smectite        heteroadduct, the smectite heteroadduct comprising the contact        product of [1] a colloidal smectite clay and [2] a        heterocoagulation reagent comprising at least one cationic        polymetallate in a liquid carrier and in an amount sufficient to        provide a slurry of the smectite heteroadduct having a zeta        potential in a range of from about positive 25 mV (millivolts)        to about negative 25 mV.        In an aspect, for example, the optional co-catalyst can be an        alkylating agent which may or may not be required for initiating        efficient olefin polymerization depending upon the particular        metallocene compound used to make the olefin polymerization        catalyst.

In a further aspect, there is provided a process for polymerizingolefins, the process comprising contacting at least one olefin monomerand a catalyst composition under polymerization conditions to form apolyolefin, wherein the catalyst composition comprises:

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined smectiteheteroadduct, the smectite heteroadduct comprising the contact productof [1] a colloidal smectite clay and [2] a heterocoagulation reagentcomprising at least one cationic polymetallate in a liquid carrier andin an amount sufficient to provide a slurry of the smectite heteroadducthaving a zeta potential in a range of from about positive 25 mV (+25millivolts) to about negative 25 mV (−25 millivolts).

These and other aspects, features, and embodiments of the compositionsincluding the support-activator and the catalyst compositions, themethods of making the compositions, and the polymerization processes andassociated methods are more fully described in the Detailed Description,the Figures, the Examples, and the claims which are provided herein.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 provides a schematic representation of an aspect of thisdisclosure, illustrating a method to prepare, wash, and isolate thesupport-activator comprising a calcined smectite heteroadduct of thisdisclosure, and contrasts this process with the method to prepare, wash,and isolate a pillared clay.

FIG. 2 provides a powder XRD (x-ray diffraction) pattern of a series ofcalcined products from combining aluminum chlorhydrate (ACH) andVolclay® HPM-20 montmorillonite. All of the samples were preparedaccording to the inventive methods according to the examples (seeExamples 18, 20-21, and 23) except for the 6.4 mmol Al/g clay sample(top), representing typically prepared Al₁₃-pillared clay (comparativeExample 5), and the starting clay itself at the 0 mmol Al/g clay sample(comparative Example 3).

FIG. 3 illustrates a zeta potential titration for the volumetricaddition of a 2.5 wt. % (weight percent) aqueous solution of aluminumchlorohydrate (ACH; measured density of 1.075 g/mL) into a 0.62 wt. %Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zetapotential versus the titrant volume (mL). The titration settings were0.5 mL per titration point, followed by an equilibration delay of 30seconds. The titrant volume indicates the cumulative volume of theaqueous aluminum chlorohydrate solution added. See also Table 4.

FIG. 4 shows the conversion of the FIG. 3 plot into a zeta potentialversus a mass ratio of aluminum to clay. Specifically, FIG. 4illustrates a zeta potential titration for the addition of a 2.5 wt. %aqueous solution of aluminum chlorohydrate (ACH; measured density of1.075 g/mL) into a 0.62 wt. % Volclay® HPM-20 bentonite aqueousdispersion, plotting the measured zeta potential versus the Al content(mmol Al/g clay). The titrant amount indicates the cumulative mmol ofaluminum of the aqueous ACH solution added.

FIG. 5 illustrates a zeta potential titration for the volumetricaddition of a 4.58 wt. % aqueous solution of UltraPAC® 290 polyaluminumchloride (empirically Al₂(OH)_(2.5)Cl_(3.5)) into a 1 wt. % Volclay®HPM-20 bentonite aqueous dispersion, plotting the measured zetapotential versus the titrant volume (mL). The titration settings were 1mL per titration point, followed by an equilibration delay of 30seconds. The titrant volume indicates the cumulative volume of theaqueous UltraPAC® 290 polyaluminum chloride solution added. See alsoTable 5.

FIG. 6 provides a zeta potential titration (adjusted) for the volumetricaddition of a 10 wt. % aqueous dispersion of NYACOL® AL27 colloidalalumina into a 0.75 wt. % Volclay® HPM-20 bentonite aqueous dispersion,plotting the measured zeta potential versus the titrant volume (mL). Thetitration settings were 1 mL per titration point from 0-27 mL and 3 mLper titration point afterwards, equilibration delay of 60 seconds. Thetitrant volume indicates the cumulative volume of the aqueous solutionof NYACOL® AL27 colloidal alumina added. See Example 11 and Table 6.

FIG. 7 illustrates a zeta potential titration for the volumetricaddition of a 2.5 wt. % aqueous solution of aluminum chlorohydrate (ACH)into a 5 wt. % aqueous dispersion of AEROSIL® 200 fumed silica, plottingthe measured zeta potential versus the titrant volume (mL). Thetitration settings were 1 mL per titration point, with an equilibrationdelay of 60 seconds. The titrant volume indicates the cumulative volumeof the aqueous solution of ACH added. See Example 37.

FIG. 8 shows the conversion of the FIG. 7 plot into a zeta potentialversus a mass ratio of aluminum to clay. Specifically, FIG. 8 provides azeta potential titration for the addition of a 2.5 wt. % aqueoussolution of aluminum chlorohydrate (ACH) into a 5 wt. % aqueousdispersion of AEROSIL® 200 fumed silica, plotting the measured zetapotential versus the Al content (mmol Al/g clay). The titrant amountindicates the cumulative mmol of aluminum of the aqueous ACH solutionadded.

FIG. 9 provides a zeta potential titration (adjusted) for the volumetricaddition of an aluminum chlorohydrate (ACH) solution-treated AEROSIL®200 fumed silica dispersion, containing 5 wt. % by silica, into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion. The titration settingswere 0.2 mL per titration point from 0-1.2 mL and 0.5 mL per titrationpoint onwards, with an equilibration delay of 30 seconds. The titrant isa colloidal species, therefore, the zeta potential was adjusted usingthe described method of Example 11 to provide the plot in FIG. 9. SeeExample 38.

FIG. 10 shows the results of a nitrogen adsorption/desorption BJH(Barrett, Joyner, and Halenda) pore volume analysis of the aluminumchlorhydrate (ACH) heterocoagulated clay of Example 18, providing a plotof pore diameter (Angstrom, Å) versus the cumulative pore volume (cubiccentimeters per gram, cc/g) for the heteroadduct. The recipe for thepreparation of this heteroadduct slurry used 1.76 mmol Al/g clay.

FIG. 11 provides the results of a nitrogen adsorption/desorption BJHpore volume analysis of a comparative sheared, then azeotroped, sampleof Volclay® HPM-20 bentonite, but without further treatment, accordingto comparative Example 3 showing values for V_(3-10 nm) that are greaterthan 55% of the cumulative pore volume V_(3-30 nm).

FIG. 12 shows the results of a nitrogen adsorption/desorption BJH porevolume analysis of an untreated sample of Volclay® HPM-20 bentonitewhich was suspended in water, evaporated, and calcined, but withoutfurther treatment according to comparative Example 1, showing values forV_(3-10 nm) that are greater than 55% of the cumulative pore volumeV_(3-30 nm).

FIG. 13 is a ¹H NMR spectrum of 7-phenyl-2-methyl-indene in CDCl₃, withcontaminant CH₂Cl₂ and water peaks identified, and showing the peakintegration values.

FIG. 14 is a ¹H NMR spectrum of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)-zirconium dichloride in CDCl₃, with thepeak integration values shown.

DETAILED DESCRIPTION OF THE DISCLOSURE

In order to more clearly define the terms and phrases used herein, thefollowing definitions are provided. To the extent that any definition orusage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

A. Definitions and Explanation of Terms

Polymetallate. The term “polymetallate”, and similar terms such as“polyoxometallate”, are used interchangeably in this disclosure to referto the water-soluble polyatomic cations that include two or more metalatoms (for example, aluminum, silicon, titanium, zirconium, or othermetals) along with at least one bridging ligand between metals such asoxo, hydroxy and/or halide ligands. The specific ligands can depend uponthe precursor and other factors, such as the process for generating thepolymetallate, the solution pH, and the like. For example, thepolymetallates of this disclosure can be hydrous metal oxides, hydrousmetal oxyhydroxides, and the like, including combinations thereof.Bridging ligands such as oxo ligands which bridge two or more metals canoccur in these species, however, polymetallates can also includeterminal oxo, hydroxyl, and/or halide ligands.

While many known polymetallate species are anionic, and the suffix“-ate” is often used to reflect an anionic species, the polymetallate(polyoxometallate) species used according to this disclosure arecationic. These materials may be referred to as compounds, species, orcompositions, but the person of ordinary skill in the art willunderstand that polymetallate compositions can contain multiple speciesin a suitable carrier such as in aqueous solution, depending upon, forexample, the solution pH, the concentration, the starting precursor fromwhich the polymetallate is generated in aqueous solution, and the like.For clarity and convenience, these multiple species are referred tocollectively as “polymetallates” or “polyoxometallates”, regardless ofwhether the compositions include or consist primarily of cationicpolyoxometallates, polyhydroxymetallates, polyoxohydroxymetallate, orspecies that include other ligands such as halides, or mixtures ofcompounds. Examples of polymetallates include but are not limited topolyaluminum oxyhydroxychlorides, aluminum chlorhydrate, polyaluminumchloride, or aluminum sesquichlorohydrate compositions, which caninclude linear, cyclic or cluster compounds. These compositions arereferred to collectively as polymetallates, although the term“polymetallate” or “polyoxometallate” are also used to described acomposition substantially comprising a single species.

Both isopolymetallates, which contain a single type of metal, andheteropolymetallates, which contain more than one type of metal (orelectropositive atoms such as phosphorus) are included in the generalterms polymetallate or polyoxometallate. For example, aluminumpolymetallates such as provided by aluminum chlorhydrate (ACH) orpolyaluminum chloride (PAC) are exemplary of a isopolymetallate. In afurther example, the polymetallates of this disclosure can be preparedfrom a first metal oxide which is subsequently treated with a secondmetal oxide, a metal halide, a metal oxyhalide, or a combination thereofin an amount sufficient to provide a colloidal suspension of aheteropolymetallate. For example, the first metal oxide can comprisesilica, alumina, zirconia and the like, including fumed silica, alumina,or zirconia, and the second metal oxide, the metal halide, or the metaloxyhalide can be obtained from an aqueous solution or suspension of themetal oxide, hydroxide, oxyhalide, or halide, such as ZrOCl₂, ZnO,NbOCl₃, B(OH)₃, AlCl₃, or a combination thereof. Therefore, whendifferent metals are employed in this preparation, the resulting speciesis considered a heteropolymetallate. Both isopolymetallates andheteropolymetallates may be referred to as simply “polymetallates”.

In a further aspect, the polymetallates according to this disclosure canbe non-alkylating toward transition metal compounds such as metallocenecompounds. That is, the subject polymetallates can be absent directmetal-carbon bonds as would be found in aluminoxanes or otherorganometallic species.

The size and number or metal ions in the polymetallate species can varyconsiderably, and as such, polymetallates can be considered to encompassboth oligomeric or polymeric species. When describing the polymetallateas “comprising”, “consisting of”, “consisting essentially of”, or being“selected from” specified materials such as polyaluminum chloride oraluminum sesquichlorohydrate, it should be understood that thepolymetallate species which form when these materials are contacted withwater or aqueous base and the like are being described according to theprecursor from which they are generated. Therefore, for convenience andfor definiteness and clarity pursuant to 35 U.S.C. § 112, thepolymetallates may be described herein according to the precursormaterials or compositions from which the cationic polymetallates aregenerated to provide the heterocoagulation reagent.

In an aspect, the polymetallate according to this disclosure can be atleast one aluminum polymetallate. Examples include, but are not limitedto, aluminum chlorhydrate (ACH), also termed aluminum chlorohydrate,which encompasses multiple water soluble aluminum species, usuallyconsidered as having the general formula Al_(n)Cl_(3n-m)(OH)_(m). Thesepolymetallate species can be referred to as aluminum oxyhydroxychloridecompounds or compositions. Another polymetallate that can be usedaccording to this disclosure is polyaluminum chloride (PAC), which isalso not a single species, but a collection of multiple aluminumpolymeric species which can include linear, cyclic, or clustercompounds, examples of which can contain from 2 to about 30 aluminumatoms, oxo, chloride, and hydroxyl groups. Other examples of aluminumpolymetallates include, but are not limited to, compounds having thegeneral formula [Al_(m)O_(n)(OH)_(x)Cl_(y)].zH₂O such as aluminumsequichlorohydrate, and cluster-type species such as Keggin ions, forexample, [AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺.7[Cl]⁻, sometimes referred to as“Al₁₃-mer” polycation. Polyaluminum chloride (PAC), for example, can beproduced by combining aqueous hydroxide with AlCl₃, and the resultingmixture of aluminum species has a range of basicities. Aluminumchlorhydrate (ACH) is generally considered the most basic, andpolyaluminum chloride (PAC) being less basic.

The clay heteroadduct or clay heterocoagulate according to thisdisclosure include the contact product of [1] a colloidal smectite clay,such as a dioctahedral smectite clay, and [2] a heterocoagulationreagent comprising at least one cationic polymetallate in a liquidcarrier such as an aqueous carrier, in which the amount used issufficient to provide a slurry of the smectite heteroadduct having azeta potential in a range of from about +25 mV to about −25 mV. Onceisolated, the smectite heteroadduct can be heated and dried and calcinedto form the support-activator as described herein. Upon calcining,additional reaction of the polymetallate which was initiallyintercalated into or associated with the smectite may occur, forexample, water may be driven off the intercalated polymetallate andadditional oxo groups may be formed. In this aspect, the term“polyoxometallate” may be particularly useful to illuminate the calcinedproduct. Regardless, the terms “polymetallate” and “polyoxometallate”are used interchangeably to describe the composition used to contact thecolloidal smectite.

The polymetallates of this disclosure may also be termed “polycations”and can include both homopolycations and heteropolycations, dependingupon whether the polycation includes a single type of metal or more thanone type of metal. For example, hydrotalcite is [Mg₆Al₂(OH)₁₆]CO₃.4H₂Owhich is a heteropolycation according to this disclosure.

Other examples of polymetallates, which are provided as exemplary only,include the ε-Keggin cations [ε—PMo₁₂O₃₆(OH)₄{Ln(H₂O)₄}₄]⁵⁺, wherein Lncan be La, Ce, Nd, or Sm. See, for example, Angew. Chem., Int. Ed. 2002,41, 2398. Other examples include the lanthanide-containing cationicheteropolyoxovanadium clusters having the general formula[Ln₂V₁₂O₃₂(H₂O)₈{Cl}]Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er.See, for example, RSC Adv. 2013. 3. 6299-6304.

Finally, reference to “at least one” cationic polymetallate is used torefer to one or more sources of the cationic polymetallate being used inpreparation of the heterocoagulation reagent. That is, even when asingle source of the cationic polymetallate is used in preparing theheterocoagulation reagent in aqueous solution, and multiple species mayresult, these multiple species can be collectively referred to as asingle or single type of cationic polymetallate. Therefore, reference tomultiple or more than one cationic polymetallate is intended to refer toone or more precursor compositions or sources of the cationicpolymetallate being used to prepare the heterocoagulation reagent.

Heterocoagulation reagent. The terms “heterocoagulation reagent”,“heterocoagulation agent”, and the like are used herein to describe acomposition comprising any positively charged oligomeric or polymericmetal oxide containing species, existing in solution, or as a colloidalsuspension which, when combined with a colloidal clay dispersion in anappropriate ratio, forms a readily filterable solid (as defined herein).“Heterocoagulation reagent” can be used interchangeably with the terms“polymetallate” or “polyoxometallate” to refer to any positively chargedoligomeric or polymeric metal oxide containing species that function toform a clay heteroadduct. Therefore, “heterocoagulation reagent”emphasizes that the composition comprising one or more cationicpolymetallate species in a liquid carrier, when used in an amountsufficient to provide a slurry having a zeta potential in a range offrom about +25 mV to about −25 mV when contacted with a colloidalsmectite clay, forms a readily filterable solid. “Heterocoagulation” isa term in the art described by Lagaly in Ullmann's Encyclopedia ofChemistry 2012. Within the context of this disclosure,“heterocoagulation” is defined as the process by which negativelycharged colloidal clay particles are combined with positively chargedspecies of a heterocoagulation reagent to form a readily filterablesolid, unless otherwise specified. Heterocoagulation is also sometimesreferred to in the art and herein as heteroaggregation, such asdescribed by Cerbelaud et al. Advances in Physics: X, 2017, vol. 2,35-53.

Heteroadduct or heterocoagulate. The clay heteroadduct or clayheterocoagulate, and similar terms such as “heterocoagulated clay” or“smectite heteroadduct” and the like refer to the contact productobtained from combining the heterocoagulation reagent and the colloidalclay. That is, the agglomerate formed by the attraction of negativelycharged colloidal clay particles with positively charged species in theheterocoagulation reagent is referred to as a “heteroadduct”. Referenceis made to Wu Cheng et al. in U.S. Pat. No. 8,642,499, which isincorporated herein by reference. In one aspect, these terms refer tothe “readily filterable” contact product of a heterocoagulation reagentand a colloidal clay, as defined herein. These terms are used todistinguish the readily filterable heterocoagulate from the contactproduct of a heterocoagulation reagent and a colloidal clay which arecombined in a ratio that provides a product is not readily filterable,for example, the product formed when following a pillared clay synthesisrecipe. In the case of a pillared clay recipe, the contact product isnot easily filterable and centrifugation is generally required in orderto isolate the pillared clay product.

When describing the formation of a heterocoagulated clay using analuminum-containing heterocoagulation reagent, and unless specifiedotherwise, the ratio of the pillaring reagent such as analuminoxychloride (also termed a heterocoagulation reagent) to clay isexpressed as mm (also mmol or millimoles) Al/g clay, indicating thenumber of millimoles of Al in the pillaring or heterocoagulation agentversus the grams of clay. Reference is made to Gu et al., Clay and clayminerals, 1990, 38(5), 493-500, which is incorporated herein byreference. Unless specified otherwise, when the pillaring oraluminoxychloride heterocoagulation reagent exists as a solublesolution, the millimoles Al are calculated based on the Al weightpercent or wt. % Al₂O₃ content provided by the manufacturer.Alternatively and unless specified otherwise, when starting with a solidform of a pillaring or heterocoagulation reagent, that is to bedispersed in a solution, the millimoles of Al are determined by theweight used in the recipe and the empirical formula provided by themanufacturer.

Readily Filterable. The terms “readily filterable”, “readily filtered”,“easily filterable”, “easily filtered or separated” and the like areused herein to describe a composition according to this disclosure inwhich the solids in a mixture containing a liquid phase can be separatedby filtration from the liquid phase without resorting to centrifugation,ultra-centrifugation, or dilute solutions of less than about 2 wt. %solids, long settling times followed by decanting the liquid away fromsolids, and other such techniques. The terms are generally used hereinto describe the clay heteroadduct that is the contact product of acolloidal smectite clay and a heterocoagulation reagent under certainconditions according to this disclosure, which does not requireisolation by centrifugation, high dilution and settling or sedimentationtanks, or ultrafiltration. Thus, a readily filterable clay heteroadductcan be isolated or separated in good yield in a matter of minutes orless, or time periods of less than about one hour, from the solublesalts and byproducts of the synthesis, by passing a slurry comprisingthe heteroadduct through conventional filtering materials, such assintered glass, metal or ceramic frits, paper, natural or syntheticmatte-fiber and the like, under gravity or vacuum filtration conditions.

This disclosure provides some specific experimental and quantitativemethods by which filterability can be assessed. For example, specificmethods of quantifying filterability of the heteroadduct slurry areprovided which demonstrate that the slurry can be considered readilyfilterable or readily filtered when prepared according to the methods ofthis disclosure. Colloids or suspensions as described by Lagaly inUlmmann's Encyclopedia of Chemistry 2012, that require longsedimentation times or ultrafiltration are not considered to be“filterable” in the context of this disclosure. The readily filterablesuspensions or slurries of this disclosure can afford clear filtratesupon filtration, while “non-readily-filterable” suspensions which takesubstantially longer to filter can contain particulate matter that isobservable as a cloudy or non-clear filtrate to the naked eye,indicative of colloidal clay dispersions. When the support-activatoraccording to this disclosure is prepared to provide a slurry of thesmectite heteroadduct having a zeta potential near the upper (positive)boundary of about +25 mV (millivolts) or near the lower (negative)boundary of about −25 mV, upon filtration of the heteroadduct, somecloudiness can be observed in the filtrate, which dimishes as thesmectite heteroadduct is prepared using ratios of colloidal smectiteclay and heterocoagulation reagent that provide a slurry having a zetapotential closer to or approaching 0 mV.

Colloid. The term “colloid”, “colloidal clay”, “colloidal solution”,“colloidal suspension” and similar terms are used as defined by GerhardLagaly in Ullmannn's Encyclopedia of Industrial Chemistry, in thechapter entitled “Colloids”, which published 15 Jan. 2007. These termsare used interchangeably.

Catalyst composition and catalyst system. Terms such as “catalystcomposition,” “catalyst mixture,” “catalyst system,” and the like areused to represent the combination of recited components which ultimatelyform, or are used to form, the active catalyst according to thisdisclosure. The use of these terms does not depend upon any specificcontacting steps, order of contacting, whether any reaction may occurbetween or among the components, or any product which may form from anycontact of any or all of the recited components. The use of these termsalso does not depend upon the nature of the active catalytic site, orthe fate of any co-catalyst, the metallocene compound(s), orsupport-activator, after contacting or combining any of these componentsin any order. Therefore, these and similar terms encompass thecombination of initial recited components or starting components of thecatalyst composition, as well as any product(s) which may result fromcontacting these initial recited starting components, regardless ofwhether the catalyst composition is heterogeneous or homogenous orincludes soluble and insoluble components. The terms “catalyst” and“catalyst system” or “catalyst composition” may be used interchangeably,and such use will be apparent to the skilled person from the context ofthe disclosure.

Catalyst activity. Unless otherwise specified, the terms “activity”,“catalyst activity”, “catalyst composition activity” and the like referto the polymerization activity of a catalyst composition comprising adried or calcined clay heteroadduct as disclosed herein, which istypically expressed as weight of polymer polymerized per weight ofcatalyst clay support-activator only, absent any transition metalcatalyst components such as a metallocene compound, any co-catalyst suchas an organoaluminum compound, or any co-activators such as analuminoxane, per hour of polymerization. In other words, the weight ofpolymer produced divided by the weight of calcined clay heteroadduct perhour, in units of g/g/hr (grams per gram per hour).

Activity of a reference or comparative catalyst composition refers tothe polymerization activity of a catalyst composition comprising acomparative catalyst composition and is based upon the weight of acomparative ion-exchanged or pillared clay or weight of the claycomponent by itself that is used to prepare clay heteroadducts. Termssuch as “increased activity” or “improved activity” describe theactivity of a catalyst composition according to this disclosure which isgreater than the activity of a comparative catalyst composition thatuses the same catalyst components such as metallocene compound andco-catalyst, except that the comparative catalyst composition utilizes adifferent support-activator or activator generally, such as a pillaredclay, or the clay component used in the catalytic reaction is not aheterocoagulated clay. For example, the increased or improved activityaccording to this disclosure includes an activity based upon thecalcined clay heteroadduct greater than or equal to about 300 grams ofpolyethylene polymer per gram of calcined heterocoagulated clay per hour(g/g/hr), using a standard set of ethylene homopolymerizationconditions. In this aspect, the standard set of ethylenehomopolymerization conditions include the following. A 2 L stainlesssteel reactor equipped with a marine type impeller is set at about 500rpm, and the slurry polymerization conditions include 1 L of purifiedisobutane diluent, 90° C. polymerization temperature, 450 total psiethylene pressure, typically 30 or 60 minute run length, metallocenecatalyst composition comprising (1—Bu-3-MeCp)₂ZrCl₂ withtriethylaluminum (TEAL) co-catalyst, optionally using the metallocene asa stock solution which contained the TEAL, which is charged in an amountto provide a metallocene-to-clay ratio of about 7×10⁻⁵ mmolmetallocene/mg calcined clay. Generally one alkyl aluminum cocatalystwas used in the polymerization runs and usually was selected from TEALor triisobutylaluminum (TIBAL).

Contact product. The term “contact product” is used herein to describecompositions wherein the components are combined together or “contacted”in any order, unless a specific order is stated or required or impliedby the context of the disclosure, in any manner, and for any length oftime. Although “contact product” can include reaction products, it isnot required for the respective components to react with one another,and this term is used regardless of any reaction which may or may notoccur upon contacting the recited components. To form a contact product,for example, the recited components can be contacted by blending ormixing or the components can be contacted by adding the components inany order or simultaneously into a liquid carrier. Further, thecontacting of any components can occur in the presence or absence of anyother component of the compositions described herein, unless otherwisestated or required or implied by the context in which the term is used.Combining or contacting the recited components or any additionalmaterials can be carried out by any suitable method. Therefore, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Similarly, theterm “contacting” is used herein to refer to materials which may beblended, mixed, slurried, dissolved, reacted, treated, or otherwisecontacted in some manner.

Pore diameter (pore size). Nitrogen adsorption/desorption measurementswere used to determine pore size and pore volume distributions using theBJH method. Based upon the International Union of Pure and AppliedChemistry (IUPAC) system for classifying porous materials (see Pure &Appl. Chem., 1994, 66, 1739-1758), and Klobes et al., National Instituteof Standards and Technology Special Publication 960-17, pore sizes aredefined as follows. “Micropore” and “microporous” as used herein refersto pores present in catalysts or catalyst supports produced according toprocesses of the disclosure having a diameter of less than 20 Å.“Mesopore” and “mesoporous” as used herein refers to pores present incatalysts or catalyst supports produced according to processes of thepresent disclosure having a diameter in a range of from 20 Å to lessthan 500 Å (that is from 2 nm to <50 nm). “Macropore” and “macroporous”as used herein refers to pores present in catalysts or catalyst supportsproduced according to processes of the present disclosure having adiameter equal to or greater than 500 Å (50 nm).

Each of the above definitions of micropore, mesopore and macropore areconsidered distinct and non-overlapping, such that pores are not countedtwice when summing up percentages or values in a distribution of poresizes (pore diameter distribution) for any given sample.

“d50” means the median pore diameter as measured by porosimetry. Thus,“d50” corresponds to the median pore diameter calculated based on poresize distribution and is the pore diameter above which half of the poreshave a larger diameter. The d50 values reported herein are based onnitrogen desorption using the well-known calculation method described byE. P. Barrett, L. G. Joyner and P. P. Halenda (“BJH”), “TheDetermination of Pore Volume and Area Distributions in PorousSubstances. I. Computations from Nitrogen Isotherms,” J. Am. Chem. Soc.,1951, 73 (1), pp 373-380.

The “median pore diameter” (MPD) can be calculated based upon, forexample, volume, surface area or based on pore size distribution data.Median pore diameter calculated by volume means the pore diameter abovewhich half of the total pore volume exists. Median pore diametercalculated by surface area means that pore diameter above which half ofthe total pore surface area exists. Similarly, median pore diametercalculated based on pore size distribution means the pore diameter abovewhich half of the pores have a larger diameter according to the poresize distribution determined as described elsewhere herein, for example,through derivation from nitrogen adsorption-desorption isotherms.

Transition metal catalyst. A “transition metal catalyst” refers to atransition metal compound or composition which can function as, or betransformed into, an active olefin polymerization catalyst whencontacted with the support-activator of this disclosure, either in itscurrent form or when contacted with a co-catalyst which is capable oftransferring or imparting a polymerization-activatable ligand to thetransition metal catalyst. The use of the term “catalyst” is notintended to reflect any specific mechanism or that the “transition metalcatalyst” itself represents an active site for catalytic polymerizationwhen it is activated or when it has been imparted with apolymerization-activatable ligand. The transition metal catalyst isdescribed according to the transition metal compound or compounds usedin the process for preparing a polymerization catalyst, and can includemetallocene compounds and defined herein, and related compounds.

Co-catalyst. A “co-catalyst” is used herein to refer to a chemicalreagent, compound, or composition which is capable of imparting a ligandto the metallocene which can initiate polymerization when themetallocene is otherwise activated with the support-activator. In otherwords, the “co-catalyst” is used herein to refer to a chemical reagent,compound, or composition which is capable of providing apolymerization-activatable ligand to a metallocene compound.Polymerization-activatable ligands include, but are not limited to,hydrocarbyl groups such as alkyls such as methyl or ethyl, aryls andsubstituted aryls such as phenyl or tolyl, substituted alkyls such asbenzyl or trimethylsilylmethyl (—CH₂SiM₃), hydride, silyl andsubstituted groups such as trimethylsilyl, and the like. Therefore, inan aspect, a co-catalyst can be an alkylating agent, a hydriding agent,a silylating agent, and the like. There are no limitations as to themechanism by which the co-catalyst provides a polymerization-activatableligand to the metallocene compound. For example, the co-catalyst canengage in a metathesis reactions to exchange an exchangeable ligand suchas a halide or alkoxide on the metallocene compound with apolymerization-activatable/initiating ligand such as methyl or hydride.In an aspect, the co-catalyst is an optional component of the catalystcomposition, for example, when the metallocene compounds alreadyincludes a polymerization-activatable/initiating ligand such as methylor hydride. In another aspect, and as understood by the person skilledin the art, even when the metallocene compound includes apolymerization-activatable ligand, a co-catalyst can be used for otherpurposes, such as to scavenge moisture from the polymerization reactoror process. According to a further aspect and as the context requires orallows, the term “co-catalyst” may refer to an “activator” or may beused interchangeably with “co-catalyst” as explained herein.

Activator. An “activator”, as used herein, refers generally to asubstance that is capable of converting a metallocene component into anactive catalyst system which can polymerize olefins, and is intended tobe independent of the mechanism by which such activation occurs. An“activator” can convert the contact product of a metallocene componentand a component that provides an activatable ligand (such as an alkyl ora hydride) to the metallocene, for example, when the metallocenecompound does not already comprise such a ligand, into a catalyst systemwhich can polymerize olefins. This term is used regardless of the actualactivating mechanism. Illustrative activators can include, but are notlimited to a support-activator, aluminoxanes, organoboron ororganoborate compounds, ionizing compounds such as ionizing ioniccompounds, and the like. Aluminoxanes, organoboron or organoboratecompounds, and ionizing compounds may be referred to as “activators” or“co-activators” when used in a catalyst composition in which asupport-activator is present, but the catalyst composition issupplemented by one or more aluminoxane, organoboron, organoborate,ionizing compounds, or other co-activators.

Support-Activator. The term “support-activator” as used herein, refersto an activator in a solid form, such as ion-exchanged-clays,protic-acid-treated clays, or pillared clays, and similar insolublesupports which also function as activators. When the support-activatoris combined with a metallocene with an activatable ligand or optionallywith a metallocene and a co-catalyst which can provide an activatableligand, provides a catalyst system which can polymerize olefins.

Ion-exchanged clay. The term “ion-exchanged clay” as used herein isunderstood by the person skilled in the art as a clay (also referred toas a “monoionic” or “monocationic” clay) in which the exchangeable ionsof a naturally-occurring or synthetic clay have been replaced by orexchanged with another selected ion or ions. Ion exchange can occur bytreatment of the naturally-occurring or synthetic clay with a source ofthe selected cation, usually from concentrated ionic solutions such as 2N aqueous solutions of the cation, including through multiple exchangesteps, for example, three exchange steps. The exchanged clay can besubsequently washed several times with deionized water to remove excessions produced by the treatment process, for example as described inSanchez, et al., Colloids and Surfaces A: Physicochemical andEngineering Aspects, 2013, 423, 1-10, and Kawamura et al., Clay and ClayMinerals, 2009, 57(2), 150-160. Generally, centrifugation is used toisolate the clay from solution between ion treatments and washings.

Metallocene compound. The term “metallocene” or “metallocene compound”as used herein, describes a transition metal or lanthanide metalcompound comprising at least one substituted or unsubstitutedcycloalkadienyl-type ligand or alkadienyl-type ligand, includingheteroatom analogs thereof, regardless of the specific bonding mode, forexample, regardless of whether the cycloalkadienyl-type ligand oralkadienyl-type ligand are bonded to the metal in an η⁵-, η³-, orη¹-bonding mode, and regardless of whether more than one of thesebonding modes is accessible by such ligands. In this disclosure, theterm “metallocene” is also used to refer to a compound comprising atleast one pi-bonded allyl-type ligand in which the η³-allyl is not partof a cycloalkadienyl-type or alkadienyl-type ligand, which can be usedas the transition metal compound component of the catalyst compositiondescribed herein. Therefore, “metallocene” includes compounds withsubstituted or unsubstituted η³ to η⁵-cycloalkadienyl-type and η³ toη⁵-alkadienyl-type ligands, η³-allyl-type ligands, including heteroatomanalogs thereof, and including but not limited to cyclopentadienylligands, indenyl ligands, fluorenyl ligands, η³-allyl ligands,pentadienyl ligands, boratabenzenyl ligands, 1,2-azaborolyl ligands,1,2-diaza-3,5-diborolyl ligands, substituted analogs thereof, andpartially saturated analogs thereof. Partially saturated analogs includecompounds comprising partially saturated η⁵-cycloalkadienyl-typeligands, examples of which include but are not limited totetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partiallysaturated indenyl, partially saturated fluorenyl, substituted analogsthereof, and the like. In some contexts, the metallocene is referred tosimply as the “catalyst,” in much the same way the term “co-catalyst” isused herein to refer to, for example, an organoaluminum compound.Therefore, a metallocene ligand can be considered in this disclosure toinclude at least one substituted or at one unsubstitutedcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl,boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl ligand,including substituted analogs thereof. For example, any substituent canbe selected independently from a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀heterohydrocarbyl, a C₁-C₂₀ organoheteryl, a fused C₄-C₁₂ carbocyclicmoiety, or a fused C₄-C₁₁ heterocyclic moiety having at least oneheteroatom selected independently from nitrogen, oxygen, sulfur, orphosphorus.

Organoaluminum compounds and organoboron compounds. The termsorganoaluminum compound and an organoboron compounds as used hereininclude neutral compounds such as AlMe₃ and BEt₃ and also includeanionic complexes such as LiAlMe₄, LiAlH₄, NaBH₄, and LiBEt₄, and thelike. Thus, unless otherwise specified, hydride compounds of aluminumand boron are include in the definitions of organoaluminum andorganoboron compounds, respectively, whether the compound is neutral oranionic.

Pillared clay. In this disclosure, a “pillared clay” is defined as aclay species in which ordered layers with basal spacing aresubstantially greater than 9 Å to 13 Å. When a powder clay sample isanalyzed using an X-ray diffraction apparatus capable of scanning 2θangles of 2° or greater, species containing such pillared ordering aretypically observed to possess a substantial peak at 2θ values between 2°to 9°. These are typically prepared by introduction of a pillaringagent, for example, an oxygen-containing inorganic cation such as anoxygen-containing cation of lanthanum, aluminum, or iron. Aluminumpillared clays are often prepared by contacting the pillaring agent withthe clay in an amount ranging from about 5 mmol Al/g clay or 6 mmol Al/gclay, up to about 30 mmol Al/g clay. Typical pillared clay preparationsmay contrast with preparations of the support-activator according tothis disclosure, in which the support-activator disclosed herein can beprepared using less than or equal to about 2.0 mmol Al/g clay, less thanor equal to about 1.7 mmol Al/g clay, less than or equal to about 1.5mmol Al/g clay, less than or equal to about 1.3 mmol Al/g clay, or lessthan or equal to about 1.2 mmol Al/g clay, but greater than about 0.75mmol Al/g clay, or greater than about 1.0 mmol Al/g clay. Therefore, inan aspect, the pillaring agent used to form a pillared clay can beselected from the same heterocoagulation reagents used to form theheterocoagulated clay of this disclosure. As explained herein, evenduring the preparation of the smectite heteroadducts as disclosedherein, some pillared clay species may be formed.

Intercalated. The terms “intercalated” or “intercalation” are terms ofthe art which indicate insertion of a material into the interlayers of aclay substrate. The terms are used herein in the manner understood bythe person of skill in the art, and as described in U.S. Pat. No4,637,992, unless otherwise noted.

Basal spacing. The term “basal spacing”, “basal d001 spacing”, or “d001spacing” when used in the context of smectite clays such asmontmorillonite, refers to the distance, usually expressed in angstromsor nanometers, between similar faces of adjacent layers in the claystructure. Thus, for example, in the 2:1 family of smectite clays,including montmorillonite, the basal distance is the distance from thetop of a tetrahedral sheet to the top of the next tetrahedral sheet ofan adjacent 2:1 layer and including the intervening octahedral sheet,with or without modification or pillaring. Basal spacing values aremeasured using X-ray diffraction analysis (XRD) of the d001 plane.Natural montmorillonite as found for example in bentonite, has a basalspacing range of from about 12 Å to about 15 Å. (See, for example, FifthNational Conference on Clays and Clay Minerals, National Academy ofSciences, National Research Council, Publication 566, 1958: Proceedingsof the Conference: “Heterogeneity In Montmorillonite”, J. L. McAtee,Jr., pp. 279-88 and Table 1 at p. 282.) The XRD test method fordetermining basal spacing is described in: Pillared Clays and PillaredLayered Solids, R. A. Schoonheydt et al., Pure Appl. Chem., 71(12),2367-2371, (1999); and U.S. Pat. No. 5,202,295 (McCauley) at column 27,lines 22-43.

Zeta potential. The term “zeta potential” as used herein refers to thedifference in electrical potential between the juncture of the Sternlayer (a layer of firmly-attached counterions which forms to neutralizethe surface charge of a colloidal particle) and diffuse layer (a cloudof loosely attached ions residing farther from the particle surface thanthe Stern layer), and the bulk solution or slurry. This property isexpressed in units of voltage, for example millivolts (mV). Zetapotential can be derived by quantifying the “Electrokinetic SonicAmplitude Effect” (ESA), which is the generation of ultrasound waves asa result of applying an electric potential across a colloidalsuspension, as described in U.S. Pat. No. 5,616,872, which isincorporated herein by reference.

Hydrocarbyl group. As used herein, the term “hydrocarbyl” group is usedaccording to the art-recognized IUPAC definition, as a univalent,linear, branched, or cyclic group formed by removing a single hydrogenatom from a parent hydrocarbon compound. Unless otherwise specified, ahydrocarbyl group can be aliphatic or aromatic; saturated orunsaturated; and can include linear, cyclic, branched, and/or fused ringstructures; unless any of these are otherwise specifically excluded. SeeIUPAC Compendium of Chemical Terminology, 2^(nd) Ed (1997) at 190.Examples of hydrocarbyl groups include, but are not limited to, aryl,alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl,aralkyl, aralkenyl, and aralkynyl groups and the like.

Heterohydrocarbyl group. The term “heterohydrocarbyl” group is used inthis disclosure to encompass a univalent, linear, branched, or cyclicgroup, formed by removing a single hydrogen atom from a carbon atom of aparent “heterohydrocarbon” molecule in which at least one carbon atom isreplaced by a heteroatom. The parent heterohydrocarbon can be aliphaticor aromatic. Examples of “heterohydrocarbyl” groups includehalide-substituted, nitrogen-substituted, phosphorus-substituted,silicon-substituted, oxygen-substituted, and sulfur-substitutedhydrocarbyl groups in which a hydrogen has been removed form a carbonatom to generate a free valence. Examples of heterohydrocarbyl groupsinclude, but are not limited to, —CH₂OCH₃, —CH₂SPh, —CH₂NHCH₃,—CH₂CH₃NMe₂, —CH₂SiMe₃, —CMe₂SiMe₃, —CH₂(C₆H₄-4-OMe), —CH₂(C₆H₄-4-NHMe),—CH₂(C₆H₄-4—PPh₂), —CH₂CH₃PEt₂, —CH₂Cl, —CH₂(2,6-C₆H₃Cl₂), and the like.

Heterohydrocarbyl encompasses both heteroaliphatic groups (includingsaturated and unsaturated groups) and heteroaromatic groups. Therefore,heteroatom-substituted vinylic groups, heteroatom-substituted alkenylgroups, heteroatom-substituted dienyl groups, and the like are allencompassed by heterohydrocarbyl groups.

Organoheteryl group. The term “organoheteryl” group is also used inaccordance with its art-recognized IUPAC definition, as univalent groupcontaining carbon, which is thus organic, but which has its free valenceat an atom other than carbon. See IUPAC Compendium of ChemicalTerminology, 2^(nd) Ed (1997) at 284. An organoheteryl group can belinear, branched, or cyclic, and includes such common groups as alkoxy,aryloxy, organothio (or organylthio), organogermanium (ororganylgermanium), acetamido, acetonylacetanato, alkylamido,dialkylamido, arylamide, diarylamido, trimethylsilyl, and the like.Groups such as —OMe, —OPh, —S(tolyl), —NHMe, —NMe₂, —N(aryl)₂, —SiMe₃,—PPh₂, —O₃S(C₆H₄)Me, —OCF₂CF₃, —O₂C(alkyl), —O₂C(aryl),—N(alkyl)CO(alkyl), —N(aryl)CO(aryl), —N(alkyl)C(O)N(alkyl)₂,hexafluoroacetonylacetanato, and the like.

Organyl group. An organyl group is used in this disclosure in accordancewith the IUPAC definition to refer to any organic substituent group,regardless of functional type, having one free valence at a carbon atom,e.g. CH₃CH₂—, ClCH₂C—, CH₃C(═O)—, 4-pyridylmethyl, and the like. Anorganyl group can be linear, branched, or cyclic, and the term “organyl”may be used in conjunction with other terms, as in organylthio- (forexample, MeS—) and organyloxy.

Heterocyclyl group. The IUPAC Compendium compares organyl groups toother groups such as heterocyclyl groups and organoheteryl groups. Theseterms are set out in the IUPAC Compendium of Chemical Terminology,2^(nd) Ed (1997) as follows, which demonstrates the convention toassociate the “-yl” suffix on the portion of the molecule or group thatbears the valence from the missing hydrogen. Thus, heterocyclyl groupsare defined as univalent groups formed by removing a hydrogen atom fromany ring atom of a heterocyclic compound. For example, both apiperidin-1-yl group and a piperidin-2-yl group shown below, wherein thelines drawn from the nitrogen atom or carbon atom represent an openvalence and not a methyl group, are heterocyclyl groups.

However, the piperidin-1-yl group is also considered an organoheterylgroup, whereas the piperidin-2-yl group is also considered aheterohydrocarbyl group. Thus, the valence of a “heterocyclyl” can occuron any appropriate cyclic atom, whereas the valence of a “organoheteryl”occurs on a heteroatom and the valence of a heterohydrocarbyl occurs ona carbon atom.

Hydrocarbylene group and hydrocarbylidene group. A “hydrocarbylene”group is also defined according to its ordinary and customary meaning,as set out in the IUPAC Compendium of Chemical Terminology, 2^(nd) Ed(1997), as a divalent group formed by removing two hydrogen atoms from ahydrocarbon, the free valencies of which are not engaged in a doublebond. Examples of hydrocarbylene groups include, for example,1,2-phenylene, 1,3-phenylene, 1,3-propandiyl (—CH₂CH₂CH₂—),cyclopentylidene (═CC₄H₈), or methylene which is bridging (—CH₂—) anddoes not form a double bond. A hydrocarbylene group in which the freevalencies are not engaged in a double bond is distinguished from ahydrocarbylidene group such as an alkylidene group.

A “hydrocarbylidene” group is a divalent group formed from a hydrocarbonby removing two hydrogen atoms from the same carbon atom, the freevalencies of which are part of a double bond. An alkylidene group is anexemplary hydrocarbylidene and is defined as a divalent group formedfrom an alkane by removing two hydrogen atoms from the same carbon atom,the free valencies of which are part of a double bond. Examples ofalkylidene groups such as ═CHMe, CHEt, ═CMe₂, ═CHPh, or methylene inwhich the methylene carbon forms a double bond (═CH₂).

Heterohydrocarbylene group and heterohydrocarbylidene group. The term“heterohydrocarbylene” group, by analogy to hydrocarbylene group, isused to refer to a divalent group formed by removing two hydrogen atomsfrom a parent heterohydrocarbon molecule, the free valencies of whichare not engaged in a double bond. The hydrogen atoms can be removed fromtwo carbon atoms, two heteroatoms, or one carbon and one heteroatom,such that the free valencies are not engaged in a double bond. Examplesof “heterohydrocarbylidene” groups include but are not limited to—CH₂OCH₂—, —CH₂NPhCH₂—, —SiMe₂(1,2-C₆H₄)SiMe₂-, —CMe₂SiMe₂—, —CH₂NCMe₃—,—CH₂CH₂PMe-, —CH₂[1,2-C₆H₃(4-OMe)]CH₂—, —and the like.

By analogy to a hydrocarbylidene, a “heterohydrocarbylidene” group is adivalent group formed from a heterohydrocarbon by removing two hydrogenatoms from the same carbon atom, the free valencies of which are part ofa double bond. Examples of heterohydrocarbylidene groups include, butare not limited to groups such as ═CHNMe₂, ═CHOPh, ═CMeNMeCH₂Ph,═CHSiMe₃, ═CHCH₂Cl, and the like.

Halide and halogen. The terms “halide” and “halogen” are used herein torefer to the ions or atoms of fluorine, chlorine, bromine, or iodine,individually or in any combination, as the context and chemistry allowsor dictates. These terms may be used interchangeably regardless ofcharge or the bonding mode of these atoms.

Polymer. The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, and thelike, derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and so forth. Therefore, anolefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as propylene, 1-butene, 1-hexene, or1-octene. If the monomer and comonomer were ethylene and 1-hexene,respectively, the resulting polymer would be categorized an asethylene/1-hexene copolymer. In like manner, the term “polymerization”includes homopolymerization, copolymerization, terpolymerization, and soforth. For example, a copolymerization process includes contacting oneolefin monomer such as ethylene and one olefin comonomer such as1-hexene to produce a copolymer. Well-known abbreviations for polyolefintypes, such as “HDPE” for high density polyethylene, may be used herein.

When the context allows or requires, the term “polymer” is used hereinto refer to inorganic compositions used in the preparation and formationof pillars in modified clays. For example, pillars are known to beformed in smectite clays based on the use of a polymeric cationichydroxy metal complexes of metals such as aluminum, zirconium, and/ortitanium, such as aluminum chlorohydroxide complexes (also known as“chlorhydrate” or “chlorhydrol”). Inorganic copolymers comprising suchcomplexes are also known. See, for example, U.S. Pat. Nos. 4,176,090 and4,248,739. Furthermore, unless otherwise expressly stated, the termpolymer is not limited by molecular weight and therefore encompassesboth lower molecular weight polymers, sometimes referred to asoligomers, as well as higher molecular weight polymers.

Procatalyst. The term “procatalyst” as used herein means a compound thatis capable of polymerizing, oligomerizing or hydrogenating olefins whenactivated by an aluminoxane, borane, borate or other acidic activator,whether a Lewis acid or a Brønsted acid, or when activated by asupport-activator as disclosed herein.

Additional Explanations of Terms. The following additional explanationsof terms are provided to fully disclosed aspects of the disclosure andclaims.

Unless specified otherwise or unless the context requires otherwise, thechemical formulas for the polymetallates used as heterocoagulationagents disclosed herein are empirical formulas. Therefore, formulas suchas (Al,Mg)₂Si₄O₁₀(OH)₂(H₂O)₈ are empirical polymetallate formulas whichcan be considered to encompass oligomeric or polymeric species, andformulas such as FeO_(x)(OH)_(y)(H₂O)_(z)]^(n+) also can be consideredto encompass oligomers or polymers in which the variable subscripts arenot required to be integers.

Several types of numerical ranges are disclosed herein, including butnot limited to, numerical ranges of a number of atoms, basal spacings,weight ratios, molar ratios, percentages, temperatures, and so forth.When disclosing or claiming a range of any type, Applicant's intent isto disclose or claim individually each possible number that such a rangecould reasonably encompass, consistent with the written description andthe context, and including the end points of the range and anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when the Applicant discloses or claims a chemical moiety thathas a certain number of carbon atoms, such as a C1 to C12 (or C₁ to C₁₂)alkyl group, or in alternative language having from 1 to 12 carbonatoms, the Applicant's intent is to refer to a moiety that can beselected independently from an alkyl group having 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, or 12 carbon atoms, as well as any range between these twonumbers (for example, a C1 to C6 alkyl group), and also including anycombination of ranges between these two numbers (for example, a C2 to C4and C6 to C8 alkyl group). Applicants reserve the right to proviso outor exclude any individual members of any such range or group, includingany sub-ranges or combinations of sub-ranges within the group, that canbe claimed according to a range or in any similar manner, if for anyreason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

In another aspect, any range of numbers recited in the specification orclaims, such as that representing a particular set of properties, unitsof measure, conditions, physical states or percentages, is intended toliterally incorporate expressly herein by reference or otherwise, anynumber falling within such range, including any subset of numbers withinany range so recited. For example, whenever a numerical range with alower limit, RL, and an upper limit RU, is disclosed, any number Rfalling within the range is specifically disclosed. In particular, thefollowing numbers R within the range are specifically disclosed:

R=RL+k(RU−RL),

wherein k is a variable ranging from 1% to 100% with a 1% increment,e.g., k is 1%, 2%, 3%, 4%, 5% . . . 50%, 51%, 52% . . . 95%, 96%, 97%,98%, 99%, or 100%. Moreover, any numerical range represented by any twovalues of R, as calculated above is also specifically disclosed.

For any particular compound disclosed herein, any general or specificstructure presented also encompasses all conformational isomers,regioisomers, and stereoisomers that may arise from a particular set ofsubstituents, unless stated otherwise. Similarly, unless statedotherwise, the general or specific structure also encompasses allenantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, aswould be recognized by a skilled artisan.

Unless otherwise stated, values or ranges may be expressed in thisdisclosure using the term “about”, for example, “about” a stated value,greater than or less than “about” a stated value, or in a range of from“about” one value to “about” another value. When such values or rangesare expressed, other embodiments disclosed include the specific recitedvalue, a range between specific recited values, and other values closeto the specific recited value. In an aspect, use of the term “about”means ±15% of the stated value, ±10% of the stated value, ±5% of thestated value, or ±3% of the stated value. For example, when the term“about” is used as a modifier for, or in conjunction with, a variable,characteristic or condition, it is intended to convey that the numbers,ranges, characteristics and conditions disclosed herein are sufficientlyflexible that practice of this disclosure by those skilled in the artusing temperatures, rates, times, concentrations, amounts, contents,properties such as basal spacing, size, including pore size, porevolume, surface area, and the like that are somewhat outside of thestated range or different from a single stated value, may achieve thedesired results as described in the application, such as the preparationof porous catalyst carrier particles having defined characteristics andtheir use in preparing active olefin polymerization catalysts and olefinpolymerization processes using such catalysts.

The terms “a,” “an,” “the”, and the like (such as “this”) are intendedto include plural alternatives such as at least one, unless otherwisespecified. For example, the disclosures of “a support-activator,” “anorganoaluminum compound,” or “a metallocene compound” are meant toencompass one, or mixtures or combinations of more than one, catalystsupport-activator, organoaluminum compound, or metallocene compound,respectively.

The term “comprising” and variations thereof such as “comprises”,“comprised of”, “having”, “including,” and the like, as recited intransitional phrases or the specification, are inclusive and open-endedand do not exclude additional, unrecited elements or method steps. Thetransitional phrase “consisting of” and variations thereof exclude anyelement, step, or ingredient not specified in the claim. Thetransitional phrase “consists essentially of” limits the scope of theclaim to the specified components or steps and those that do notmaterially affect the basic and novel characteristics of the claimedinvention. Unless otherwise indicated, describing a compound orcomposition as “consisting essentially of” should not be construed as“comprising,” as this phrase is intended to describe the recitedcomponent that includes materials which do not significantly altercomposition or method to which the term is applied. For example, aprecursor or catalyst component can consist essentially of a materialwhich can include impurities commonly present in a commercially producedsample of the material when prepared by a certain procedure. When aclaim includes different features and/or feature classes (for example, amethod step, feedstock features, and/or product features, among otherpossibilities), the transitional terms comprising, consistingessentially of, and consisting of apply only to feature class to whichis utilized and it is possible to have different transitional terms orphrases utilized with different features within a claim. For example amethod can comprise several recited steps (and other non-recited steps)but utilize a catalyst system preparation consisting of specific oralternatively consisting essentially of specific steps but utilize acatalyst system comprising recited components and other non-recitedcomponents. When compositions and processes are described in terms of“comprising” various components or steps, the compositions and processescan also “consist essentially of” or “consist of” the various componentsor process steps.

Unless otherwise defined with respect to a specific property,characteristic or variable, the terms “substantial” and “substantially”as applied to any criteria such as a property, characteristic orvariable, means to meet the stated criteria in sufficient measure thatone skilled in the art would understand that the benefit to be achieved,or the condition or property value desired is met. For example, the term“substantially” may be used when describing a metallocene catalyst orcatalyst system which is substantially free of or substantially absentan aluminoxane, a borate activator, a protic-acid-treated clay, or apillared clay. In other words, the terms “substantial” and“substantially” serves reasonably to describe the subject matter so thatits scope will be understood by persons skilled in the relevant art andto distinguish the claimed subject matter from any prior art. In oneaspect, “substantially free” can be used to describe a composition inwhich none of the recited component the composition is substantiallyfree of was added to the composition, and only impurity amounts such asamounts derived from the purity limits of the other components orgenerated as a byproduct are present. In a further aspect, when acomposition is said to be “substantially free” of a particularcomponent, the composition may have less than 20 wt. % of the component,less than 15 wt. % of the component, less than 10 wt. % of thecomponent, less than 5 wt. % of the component, less than 3 wt. % of thecomponent, less than 2 wt. % of the component, less than 1 wt. % of thecomponent, less than 0.5 wt. % of the component, or less than 0.1 wt. %of the component.

The terms “optionally”, “optional” and the like with respect to a claimelement are intended to mean that the subject element is required, oralternatively, is not required, and both alternatives are intended to bewithin the scope of the claim, and it is envisioned that the claim canencompass either or both alternatives.

References to the Periodic Table or groups of elements within thePeriodic Table refer to the Periodic Table of the Elements, published bythe International Union of Pure and Applied Chemistry (IUPAC), publishedon-line at http://old.iupac.org/reports/periodic_table/; version dated19 Feb. 2010. Reference to a “group” or “groups” of the Periodic Tableas reflected in the Periodic Table of Elements using the IUPAC systemfor numbering groups of elements as Groups 1-18. To the extent that anyGroup is identified by a Roman numeral according, for example, to thePeriodic Table of the Elements as published in “Hawley's CondensedChemical Dictionary” (2001) (the “CAS” system) it will further identifyone or more element of that Group so as to avoid confusion and provide across-reference to the numerical IUPAC identifier.

Various patents, publications and documents are disclosed and referencedherein. Each reference cited in this disclosure is incorporated hereinby reference in its entirety, whether a patent, a publication, or otherdocument, and unless otherwise indicated.

References which may provide some background information related to thisdisclosure include, for example, U.S. Pat. Nos. 3,962,135; 4,367,163;5,202,295; 5,360,775; 5,753,577; 5,973,084; 6,107,230; 6,531,552;6,559,090; 6,632,894; 6,943,224; 7,041,753; 7,220,695; 9,751,961; andU.S. Patent Application Publication Nos. 2018/0142047 and 2018/0142048;each of which is incorporated by reference herein in its entirety.Additional publications which may provide some background informationrelated to this disclosure include:

-   -   Gu, B.; Doner, H. E., Clay and Clay Minerals, 1991, 38(5),        493-500;    -   Covarrubias et al., Applied Catalysis A: General, 347(2), 15        Sep. 2008, 223-233;    -   Tayano et al., Clay Science, 2016, 20, 49-58;    -   Tayano et al., Macromolecular Reaction Engineering, 2017(11),        201600017; Journal of Molecular Catalysis A: Chemical, 2016,        420, 228-236; Clay Science, 2016, 20, 49-58;    -   Finevich et al., Russian Journal of General Chemistry 2007,        77(12), 2265-2271;    -   Bibi, Singh, and Silvester, Applied Geochemistry, 2014, 51,        170-183;    -   Sharma et al., Journal of Material Science, 2018, 53,        10095-10110;    -   Okada et al., Clay Science, 2003, 12, 159-163;    -   Sucha et al., Clay Minerals, 1996, 31, 333-335;    -   Vlasova et al., Science of Sintering, 2003, 35, 155-166;    -   Kline and Fogler, Industrial & Engineering Chemistry        Fundamentals, 1981, 20(2), 155-161;    -   Ocelli, Clay and Clay Minerals, 2000, 48(2), 304-308;    -   Kooli, Microporous and Mesoporous Materials; 2013, 167, 228-236;    -   Pergher and Bertella, Materials, 2017, 10, 712; and    -   Tsvetkov et al., Clay and Clay Minerals, 1990, 38(4), 380-390;        each of which is incorporated by reference herein in its        entirety.

B. General Description

The support-activator of this disclosure can be formed by starting witha slurry of an expanding-type clay in a liquid carrier, such as smectiteor dioctahedral smectite clay, and contacting the clay in the slurrywith a heterocoagulation reagent, which comprises at least one cationicpolymetallate made under the conditions specified herein. Aheterocoagulated clay forms which can be isolated very conveniently by afiltration and subsequently dried and calcined, to provide asupport-activator that is useful to support and activate metallocenecatalyst toward olefin polymerization. Formation of the clayheteroadduct in good yield can be effected by controlling the ratio oramount of heterocoagulation reagent used relative to the clay, which ismeasured by a zeta potential measurement of the slurry in which the clayheteroadduct is formed. Thus, the clay heteroadduct comprises thecontact product in a liquid carrier of [1] a smectite clay such as acolloidal smectite clay and [2] a heterocoagulation reagent comprisingat least one cationic polymetallate and in an amount sufficient toprovide a slurry of the resulting clay heteroadduct having a zetapotential in a range of from about positive 25 mV (millivolts) to aboutnegative 25 mV.

When a smectite clay is contacted with a heterocoagulation reagent in aliquid carrier using a greater number of moles of cationic polymetallateper gram of clay than specified immediately above, such that theresulting slurry has a zeta potential greater than about +25 mV, whichwith a cationic polymetallate such as aluminum chlorhydrate (ACH) andcolloidal smectite clay can occur when using a recipe of greater thanabout 2.3 mmol Al/g clay, greater than about 2.5 mmol Al/g clay, greaterthan about 2.7 mmol Al/g clay, or greater than about 3.0 mmol Al/g clay(millimoles of Al per gram of clay), large amounts of the correspondingpillared clay can form. While a slurry of the desired smectiteheteroadduct can include some corresponding pillared clay as observed bypowder X-ray diffraction (XRD), and formation of some pillared clay issecondary or incidental to the support-activator formation, asupport-activator having too high a concentration of pillared clay ascompared to the clay heteroadduct results in a loss of the readyfilterability of the slurry, such that the ease of isolation of thesupport-activator is compromised. When a smectite clay is contacted witha heterocoagulation reagent in a liquid carrier using a smaller numberof moles of cationic polymetallate per gram of clay, such that theresulting slurry has a zeta potential less than about -25 mV, which whenusing a cationic polymetallate aluminum chlorhydrate (ACH) and colloidalsmectite clay can occur at less than about 0.5 mmol Al/g clay, less thanabout 0.6 mmol Al/g clay, or less than about 0.8 mmol Al/g clay, or insome cases, less than about 1.0 mmol Al/g clay (millimoles of Al pergram of clay), a small amount of the clay heteroadduct is formed and asubstantial amount of the colloidal smectite clay remains.

It has also been unexpectedly discovered that, in contrast to pillaredclay support-activators and similar clay-based activators used tosupport and activate metallocene catalysts, the clay heteroadductsupport-activator of this disclosure can be used with few or nosubsequent washing steps following isolation by filtration. That is, theisolated heteroadduct support-activator can be used directly in catalystformation with a metallocene, and co-catalysts such as aluminum alkylsif desired, without extensive or time-consuming purification, washing,or other such purification stages commonly used in other clay-basedsupports. This advantage can provide a substantial economic advantageand enhanced ease of use when preparing olefin polymerization catalysts.

Accordingly, in one aspect, this disclosure provides a support-activatorcomprising an isolated smectite heteroadduct, the smectite heteroadductcomprising the contact product in a liquid carrier of [1] a colloidalsmectite clay and [2] a heterocoagulation reagent comprising at leastone cationic polymetallate and in an amount sufficient to provide aslurry of the smectite heteroadduct having a zeta potential in a rangeof from about positive 25 mV (millivolts) to about negative 25 mV.

This disclosure also provides, in another aspect, a method of making asupport-activator comprising a smectite heteroadduct, the methodcomprising:

-   -   a) providing a colloidal smectite clay;    -   b) contacting in a liquid carrier the colloidal smectite clay        with a heterocoagulation reagent comprising at least one        cationic polymetallate and in an amount sufficient to provide a        slurry of a smectite heteroadduct having a zeta potential in a        range of from about positive 25 mV (millivolts) to about        negative 25 mV.        This method can further comprise the step of c) isolating the        smectite heteroadduct from the slurry.

According to a further aspect, this disclosure provides a catalystcomposition for olefin polymerization, the catalyst compositioncomprising:

-   -   a) at least one transition metal catalyst, such as a metallocene        compound;    -   b) optionally, at least one co-catalyst; and    -   c) at least one support-activator comprising a calcined smectite        heteroadduct, the smectite heteroadduct comprising the contact        product of [1] a colloidal smectite clay and [2] a        heterocoagulation reagent comprising at least one cationic        polymetallate in a liquid carrier and in an amount sufficient to        provide a slurry of the smectite heteroadduct having a zeta        potential in a range of from about positive 25 mV (millivolts)        to about negative 25 mV.

In yet a further aspect, there is provided a method of making an olefinpolymerization catalyst, the method comprising contacting in any order:

-   -   a) at least one transition metal catalyst, such as a metallocene        compound;    -   b) optionally, at least one co-catalyst; and    -   c) at least one support-activator comprising a calcined smectite        heteroadduct as described according to this disclosure.

Still another aspect of this disclosure is a process for polymerizingolefins comprising contacting at least one olefin monomer and a catalystcomposition under polymerization conditions to form a polyolefin,wherein the catalyst composition comprises:

a) at least one transition metal catalyst, such as a metallocenecompound;

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined smectiteheteroadduct, as described herein.

Reference is made to the Examples, data, and Aspects of the Disclosuresection of this written description in which detailed information of thevarious aspects and embodiments are set out for making and using thesupport-activator and catalyst compositions described herein. Thefollowing sections set out some specific details in the components usedto prepare the catalyst compositions and using the catalyst compositionsto polymerize olefins.

C. Colloidal Smectite Clays

In addition to the Definitions section, the following disclosureprovides additional information related to the smectite clays.

An expanding-type clay, such as smectite or the 2:1 dioctahedralsmectite clay, or a combination of expanding-type clays, can be used inthe preparation of the support-activator described herein. Theseexpanding-type clays may be described as phyllo silicates orphyllosilicate clays, because certain members of the clay minerals groupof the phyllosilicates can be used. Suitable starting clays can includethe layered, naturally occurring or synthetic smectites. Starting clayscan also include the dioctahedral smectite clays. Further, suitablestarting clays may also include clays such as montmorillonites,sauconites, nontronites, hectorites, beidellites, saponites, bentonites,or any combination thereof. Smectites are 2:1 layered clay minerals thatcarry a lattice charge and can expand when solvated with water andalcohols. Therefore, suitable starting clays can include, for example,the monocation exchanged, dioctahedral smectites, such as thelithium-exchanged clays, sodium-exchanged clays, or potassium-exchangedclays, or a combination thereof.

Water can also be coordinated to the layered clay structural units,either associated with the clay structure itself or coordinated to thecations as a hydration shell. When dehydrated, the 2:1 layered clayshave a repeat distance or d001 basal spacing of from about 9 Å(Angstrom) to about 12 Å (Angstrom) in the powder X-Ray Diffraction(XRD); or alternatively, in a range of from about 10 Å (Angstrom) toabout 12 Å (Angstrom) in the powder X-Ray Diffraction (XRD).

The layered smectite clays are termed 2:1 clays, because theirstructures are “sandwich” structures which include two outer sheets oftetrahedral silicate and an inner sheet of octahedral alumina which issandwiched between the silica sheets. Therefore, these structures arealso referred to as “TOT” (tetrahedral-octahedral-tetrahedral)structures. These sandwich structures are stacked one upon the other toyield a clay particle. This arrangement can provide a repeated structureabout every nine and one-half angstroms (A), as compared with thepillared or intercalated clays produced by the insertion of “pillars” ofinorganic oxide material between these layers to provide a larger spacebetween the natural clay layers.

In an aspect, the clay used to prepare the support-activator can be acolloidal smectite clay. Thus, the smectite clay can have an averageparticle size of less than about 10 μm (microns), less than about 5 μm,less than about 3 μm, less than 2 μm, or less than 1 μm, wherein theaverage particle size is greater than about 15 nm, greater than about 25nm, greater than about 50 nm, or greater than about 75 nm. That is, anyranges of clay particle sizes between these recited numbers aredisclosed. While clays that are unable to give colloidal suspensions canbe used, these are less preferred than the colloidal clays.

In one aspect, the clay used to prepare the support-activator can beabsent a bivalent or trivalent ion exchanged smectite, for example,Mg-exchanged or Al-ion exchanged montmorillonite which are described inU.S. Pat. No. 6,531,552. In another aspect, the clay used to prepare thesupport-activator can be absent mica or synthetic hectorite, asdescribed in U.S. Pat. Nos. 6,531,552 and 5,973,084. In a furtheraspect, the clay used to prepare the support-activator can be absent atrioctahedral smectite or can be absent vermiculite.

In an aspect, the smectite clay can also comprise structural unitscharacterized by the following formula:

(M^(A)IV)₈(M^(B)VI)_(p)O₂₀(OH)₄; wherein

-   -   a) M^(A)IV is a four-coordinate Si⁴⁺, wherein the Si⁴⁺ is        optionally partially substituted by a four-coordinate cation        that is not Si⁴⁺ (for example, the cation that is not Si⁴⁺ can        be selected independently from Al³⁺, Fe³⁺, P⁵⁺, B³⁺, Ge⁴⁺, Be²⁺,        Sn⁴⁺, and the like);    -   b) M^(B)VI is a six-coordinate Al³⁺ or Mg²⁺, wherein the Al³⁺ or        Mg²⁺ is optionally partially substituted by a six-coordinate        cation that is not Al³⁺ or Mg²⁺ (for example, the cation that is        not Al³⁺ or Mg²⁺ can be selected independently from Fe³⁺, F²⁺,        Ni²⁺, Co²⁺, Li⁺, Zn²⁺, Mn²⁺, Ca²⁺, Be²⁺, and the like);    -   c) p is four for cations with a +3 formal charge, or p is 6 for        cations with a +2 formal charge; and    -   d) any charge deficiency that is created by the partial        substitution of a cation that is not Si⁴⁺ at M^(A)IV and/or any        charge deficiency that is created by the partial substitution of        a cation that is not Al³⁺ or Mg²⁺ at M^(B)VI is balanced by        cations intercalated between structural units (for example, the        cations intercalated between structural units can be selected        from monocations, dications, trications, other multications, or        any combination thereof.

The Examples, data, and Aspects of the Disclosure section provideadditional detailed information of the various aspects and embodimentsof the smectite clay.

D. Cationic Polymetallates Used for Heterocoagulation Reagents

In addition to the Definitions section and the Aspects of theDisclosure, the following additional information further describes thecationic polymetallates.

As explained in the Definitions section, the term “polymetallate”, andsimilar terms such as “polyoxometallate” refer to the polyatomic cationsthat include two or more metals (for example, aluminum, silicon,titanium, zirconium, or other metals) along with at least one bridgingligand between metals such as oxo, hydroxy and/or halide ligands. Forexample, the polymetallates can be hydrous metal oxides, hydrous metaloxyhydroxides, and the like, and can include bridging ligands such asoxo ligands which bridge two or more metals can occur in these species,and can also include terminal oxo, hydroxyl, and/or halide ligands.While many polymetallate species are anionic, and the suffix “-ate” isoften used to reflect an anionic species, the polymetallate(polyoxometallate) compounds used according to this disclosure arecationic.

The heterocoagulation reagents of this disclosure can bepositively-charged species that when combined in the appropriate ratiowith a colloidal suspension of clay form a coagulate which is readilyfiltered and easily washed. The positively charged species includesoluble polyoxometallate, polyhydroxylmetallate andpolyoxohydroxymetallate cations, and related cations partially halidesubstituted, such as polyaluminum oxyhydroxychlorides or aluminumchlorhydrate or polyaluminum chloride species that are linear, cyclic orcluster compounds. These compounds are referred to collectively aspolymetallates. The latter aluminum compounds can contain from about 2to about 30 aluminum atoms.

Useful heterocoagulation reagents also include any colloidal speciesthat are characterized by a positive zeta potential when dispersed in anaqueous solvent or in a mixed aqueous and organic (for example, alcohol)solvent. For example, useful dispersions of the heterocoagulationreagents can exhibit greater than (>) +20 mV (positive 20 mV) zetapotential, greater than +25 mV zeta potential, or greater than +30 mVzeta potential. While the starting colloidal clay may include monovalentions or species such as protons, lithium ions, sodium ions, or potassiumions, at least a portion, some, most, substantially all, or all of theseions are replaced by the heterocoagulation reagents during formation ofthe readily filterable clay heteroadduct. As discussed below, protons,lithium ions, sodium ions, or potassium ions and the like do not affordthe filterability provided by the cationic polymetallates of thisdisclosure. This feature can be observed by the long filtration timesthat result when preparing and attempting to isolate the hydrochloricacid-treated support-activators, such as in Examples 40 and 41.

Further, unlike treatments that use strong, concentrated acids to leachAl ions from montmorillonite, the formation of the clay heteroadductdoes not leach Al ions from the clay. When using aluminum-containingheterocoagulation reagents such as ACH or PAC, the aluminum content ofthe support-activator is actually increased over that of the startingclay, albeit in amounts far less than the aluminum content of thecorresponding pillared clay.

In an aspect, the heterocoagulation reagent can comprise a colloidalsuspension of boehmite (an aluminum oxide hydroxide) or a metal oxidesuch as a fumed metal oxide which affords a positive zeta potential (forexample, fumed alumina). In another aspect, the heterocoagulationreagent can comprise a chemically-modified or chemically-treated metaloxide, for example an aluminum chlorhydrate-treated fumed silica, suchthat when in suspension, the chemically-treated metal oxide affords apositive zeta potential, as described below. In a further aspect, theheterocoagulation reagent may be generated by treating a metal oxide ormetal oxide hydroxide and the like in a fluidized bed with reagentswhich will afford a positive zeta potential when the agent is dispersedin a suspension. The heterocoagulation agent can exhibit a positivevalue greater than +20 mV prior to combination with the phyllosilicateclay component.

In an aspect, the cationic polymetallate can include a first metal oxidewhich is chemically-treated with a second metal oxide, a metal halide, ametal oxyhalide, or a combination thereof in an amount sufficient toprovide a colloidal suspension of the chemically-treated first metaloxide having a positive zeta potential, for example, a zeta potential ofgreater than positive 20 mV (millivolts). That is, thechemically-treated first metal oxide is the contact product of the firstmetal oxide with [1] a second metal oxide, that is, another differentmetal oxide, [2] a metal halide, [3] a metal oxyhalide, or [4] acombination thereof. For example, the first metal oxide which ischemically-treated can comprise fumed silica, fumed alumina, fumedsilica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumedzirconia, fumed ceria, and the like, or any combination thereof. Thesecond metal oxide, the metal halide, or the metal oxyhalide can beobtained from an aqueous solution or suspension of a metal oxide,hydroxide, oxyhalide, or halide, such as ZrOCl₂, ZnO, NbOCl₃, B(OH)₃,AlCl₃, or a combination thereof. For example, treatment may consist ofdispersing the fumed oxide in a solution of aluminum chlorhydrate. Inthe case of fumed silica, which in suspension may exhibit a negativezeta potential, after treatment with aluminum chlorhydrate thesuspension of the chemically-treated fumed silica exhibits a positivezeta potential of greater than about +20 mV.

In another aspect, the cationic polymetallate composition can compriseor be selected from [1] fumed silica, fumed alumina, fumedsilica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumedzirconia, fumed ceria, or any combination thereof, which ischemically-treated with [2] polyaluminum chloride, aluminumchlorhydrate, aluminum sesquichlorohydrate, polyaluminumoxyhydroxychloride, or any combination thereof. For example, thecationic polymetallate composition can comprise or be selected fromaluminum chlorhydrate-treated fumed silica, aluminumchlorhydrate-treated fumed alumina, aluminum chlorhydrate-treated fumedsilica-alumina, or any combination thereof.

While not intending to be theory-bound, it is thought that the treatedmetal oxide may form a coreshell structure of a positively charged shelland negative core, or a continuous structure of intermixed negative andpositive regions or atoms, such that the surface exhibits a positivezeta potential of greater than about +20 mV. Some fumed metal oxides,such as fumed alumina, may already exhibit a positive zeta potentialbefore chemical treatment. Nevertheless, fumed metal oxides whichpossess no zeta potential, or a positive zeta potential less than about+20 mV, may also be chemically treated with species, such as aluminumchlorohydrate and the like, after which treatment, a colloidalsuspension having a zeta potential greater than about +20 mV can beobtained.

In another aspect, the heterocoagulation reagent can include a mixtureof metal oxides formed in the fuming process, or subsequent to thefuming process, that because of their composition, exhibits a positivezeta potential. An example of this type fumed oxide is fumedsilica-alumina.

In another embodiment the heterocoagulation reagent may include anycolloidal inorganic oxide particles such as described by Lewis, et al.in U.S. Pat. No. 4,637,992, which is incorporated herein by reference,such as colloidal ceria or colloidal zirconia or any positively chargedcolloidal metal oxide disclosed therein. In another aspect, theheterocoagulation reagent may comprise magnetite or ferrihydrite. Forexample, the cationic polymetallate can comprise or be selected fromboehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia,magnetite, ferrihydrite, any positively charged colloidal metal oxide,or any combination thereof.

In another aspect, the heterocoagulation reagents can include a cationicoligomeric or polymeric aluminum species in solution, such as aluminumchlorohydrate, also known as aluminum chlorhydrate (ACH), polyaluminumchloride (PAC), aluminum sesquichlorohydrate, or any combination ormixture thereof. For example, the cationic polymetallateheterocoagulation reagent can include or be selected from an aluminumspecies or any combinations of species having the empirical formula:

Al₂(OH)_(n)Cl_(m)(H₂O)_(x),

-   -   wherein n+m=6, and x is a number from 0 to about 4.        In one aspect, the cationic polymetallate can comprises or can        be selected from aluminum species having the formula        [AlO₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺, which is the so-called “Al₁₃-mer”        polycation and which is thought to be the precursor to Al₁₃        pillared clays.

When aluminum chlorhydrate is used as the heterocoagulation reagent orchemical treatment reagent for treating other metal oxides, aluminumchlorhydrate (ACH) solution or solid powder from commercial sources canbe utilized. Aluminum chlorhydrate solutions may be referred to aspolymeric cationic hydroxy aluminum complexes or aluminumchlorhydroxides, which refers to the polymers formed from a monomericprecursor having the general empirical formula 0.5[Al₂(OH)₅Cl(H₂O)₂].Preparation of aluminum chlorhydrate solution is described in U.S. Pat.Nos. 2,196,016 and 4,176,090, which are incorporated herein byreference, and can involve treating aluminum metal with hydrochloricacid in amounts which produce a composition having the formula indicatedabove.

Alternatively, the aluminum chlorhydrate solutions may be obtained usingvarious sources of aluminum such as alumina (Al₂O₃), aluminum nitrate,aluminum chloride or other aluminum salts and treatment with acid orbase. The numerous species that can be present in such solutions,including the tridecameric [AlO₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺ (Al₁₃-mer)polycation, are described in Perry and Shafran, Journal of InorganicBiochemistry, 2001, 87, 115-124, which is incorporated herein byreference. The species disclosed in this study, either individually orin combination, which are present in such solutions can be used ascationic polymetallates for heterocoagulation of the smectite clay.

In one aspect, aqueous aluminum chlorhydrate solutions used according tothis disclosure can have an aluminum content, calculated or expressed asthe weight percent of Al₂O₃, in a range of from about 15 wt. % to about55 wt. %, although more dilute concentrations can be used. Using moredilute solutions can be accompanied by adjusting other reactionconditions such as time and temperature, as will be appreciated by theperson of ordinary skill in the art. Alternative aluminum concentrationsin aqueous aluminum polymetallate solutions such as aqueous aluminumchlorhydrate solutions, expressed as the weight percent of Al₂O₃, caninclude: from about 0.1 wt. % to about 55 wt. % Al₂O₃; from about 0.5wt. % to about 50 wt. % Al₂O₃; from about 1 wt. % to about 45 wt. %Al₂O₃; from about 2 wt. % to about 40 wt. % Al₂O₃; from about 3 wt. % toabout 37 wt. % Al₂O₃; from about 4 wt. % to about 35 wt. % Al₂O₃; fromabout 5 wt. % to about 30 wt. % Al₂O₃; or from about 8 wt. % to about 25wt. % Al₂O₃; each range including every individual concentrationexpressed in tenths (0.1) of a weight percentage encompassed therein,and including any subranges therein. For example, the recitation of fromabout 0.1 wt. % to about 30 wt. % Al₂O₃ includes the recitation of from10.1 wt. % to about 26.5 wt. % Al₂O₃. When convenient, solidpolymetallate aush as solid aluminum chlorhydrate can be used and addedto the slurry of the colloidal clay when preparing the heterocoagulate.Therefore, the concentrations disclosed above are not limiting butrather exemplary.

In one aspect, the cationic polymetallate can comprise or can beselected from an oligomer prepared by copolymerizing (co-oligomerizing)soluble rare earth salts with a cationic metal complex of at least oneadditional metal selected from aluminum, zirconium, chromium, iron, or acombination thereof, according to U.S. Pat. No. 5,059,568, which isincorporated herein by reference, for example, where the at least onerare earth metal can be cerium, lanthanum, or a combination thereof. Inan aspect, the heterocoagulation reagent can comprise an aqueoussolution of lanthanides and Al₁₃ Keggin ions, such as described byMcCauley in U.S. Pat. No. 5,059,568. However, the calcinedclay-heteroadducts of the present disclosure prepared using the McCauleytype polymetallates do not afford a uniform intercalated structure withbasal spacings of greater than 13 Å (Angstroms). Though not wishing tobe bound by theory, it is thought that this observation may result fromthe much smaller amount of Ce—Al heterocoagulation reagent-to-colloidalclay ratio used according to this disclosure. This smaller amount arisesby the conditions of contacting the smectite clay and theheterocoagulation reagent in an amount sufficient to provide a slurry ofthe smectite heteroadduct having a zeta potential in a range of fromabout +25 mV (millivolts) to about −25 mV.

In further aspects, exemplary polymetallates of this disclosure caninclude: [1] the ε-Keggin cations [ε—PMo₁₂O₃₆(OH)₄{Ln(H₂O)₄}₄]⁵⁺,wherein Ln can be La, Ce, Nd, or Sm; and [2] the lanthanide-containingcationic heteropolyoxovanadium clusters having the general formula[Ln₂V₁₂O₃₂(H₂O)₈{Cl}]Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er.

In another aspect, the heterocoagulation agent may be a layered doublehydroxide, such as a magnesium aluminum hydroxide nitrate as describedby Abend et al., Colloid Polym. Sci. 1998, 276, 730-731, or synthetichematite, hydrotalcite, or other positively charged layered doublehydroxides, including but not limited to those described in U.S. Pat.No. 9,616,412, which are incorporated herein by reference. Thus, thecationic polymetallate used as a heterocoagulation reagent can be alayered double hydroxide or a mixed metal layered hydroxide. Forexample, the mixed metal layered hydroxide can be selected from a Ni—Al,Mg—Al, or Zn—Cr—Al type having a positive layer charge. In anotheraspect, the layered double hydroxide or mixed metal layered hydroxidecan comprise or can be selected from magnesium aluminum hydroxidenitrate, magnesium aluminum hydroxide sulfate, magnesium aluminumhydroxide chloride, Mg_(x)(Mg,Fe)₃(Si,Al)₄O₁₀(OH)₂(H₂O)₄ (x is a numberfrom 0 to 1, for example, about 0.33 for ferrosaponite),(Al,Mg)₂Si₄O₁₀(OH)₂(H₂O)₈, synthetic hematite, hydrozincite (basic zinccarbonate) Zn₅(OH)₆(CO₃)₂, hydrotalcite [Mg₆Al₂(OH)₁₆]CO₃.4H₂O, tacovite[Ni₆Al₂(OH)₆]CO₃.4H₂O, hydrocalumite [Ca₂Al(OH)₆]OH.6H₂O, magaldrate[Mg₁₀A₁₅(OH)₃₁](SO₄)₂.mH₂O, pyroaurite [Mg₆Fe₂(OH)₁₆]CO₃.4.5H₂O,ettringite [Ca₆Al₂(OH)₁₂](SO₄)₃.26H₂O, or any combination thereof.

In still a further aspect, the heterocoagulation reagent can includeaqueous solutions of Fe polycations, as described by Oades, Clay andClay Minerals, 1984, 32(1), 49-57, or described by Cornell andSchwertmann in “The Iron Oxides: Structure, Properties, Reactions,Occurrences and Uses”, 2003, Second Edition, Wiley VCH. The cationicpolymetallate can comprise or can be selected from an iron polycationhaving an empirical formula FeO_(x)(OH)_(y)(H₂O)_(z)]^(n+), wherein 2x+yis less than (<) 3, z is a number from 0 to about 4, and n is a numberfrom 1 to 3.

The use of cations such as protons, lithium ions, sodium ions, orpotassium ions and the like such as described in Example 40 and Example41 do not afford clay heteroadducts as provided by the cationicpolymetallates of this disclosure, for example, these acid-treated claysgenerally are not readily filterable. Though not wishing to be bound bytheory, it is thought that monovalent ions such as protons from HCl orH₂SO₄ in aqueous solutions, such as described by Nakano et al. in U.S.Pat. No. 6,531,552 and references therein, which are incorporated hereinby reference, cannot form stable, readily filterable heterocoagulatedclay adducts whether using dilute or concentrated acid. Colloidaldispersions of smectite, such as bentonites or montmorillonites, have apermanent negative charge, and thus exhibit a permanent negative zetapotential even at low pH. Again, while not intending to be theory-bound,at the high acid concentrations of low pH (<3), colloidal dispersions ofsmectites become less negative, and may even approach a zeta potentialof about negative 30 mV (−30 mV). (See Duran et al., Journal of Colloidand Interface Science, 2000, 229, p 107-117, which is incorporatedherein by reference.) However, before the colloidal clay can approach orattain a neutralized or near-neutralized surface charge, it is thoughtthat the clay structure itself is destroyed through peptization of theoctahedral alumina layer. (See Tayano et al.; Macromolecular ReactionEngineering, 2017, 11, 201600017 and Clay Science 2016, 20, 49-58, eachof which is incorporated herein by reference.) The leaching of theoctahedral alumina layer from the TOT structure and the dissolution ofclay into the strongly acidic solutions are described, for example, in:U.S. Pat. No. 3,962,135; Bibi, Singh, and Silvester, in “Dissolutionkinetics of kaolinite, illite and montmorillonite under acid-sulfateconditions: a comparative study”, prepared for Clay Minerals, Chapter 4(manuscript accessed athttps://seslibrary.usyd.edu.au/bitstream/handle/2123/8647/Chapter%2046_Dissolution%20of%20illite,%20kaolinite,%20montmorillonite.pdf?sequence=5) and also athttps://pdfs.semanticscholar.org/6836/3c9c293dfd4255f9ad88678e1770c63384d3.pdf,and in Dudkin et al., Chemistry for Sustainable Development, 2004, 12,327-330; and Okada, et al., Clay Science, 2003, 12, 159-165, each ofwhich is incorporated herein by reference.

While not wishing to be bound by theory, it has been observed that theaddition of other, non-proton monovalent cations such as lithium, sodiumor potassium ions, by way of their respective salts, to a point whereflocculation of colloidal smectite particles can occur is thought to bedue to shielding and reduction of the columbic repulsion betweensmectite particles. The concentration of monocations at whichcoagulation occurs is termed the critical coagulation concentration, andthe concentration of the monovalent cations required to achievecoagulation is generally significantly greater than the concentrationsneeded when using divalent or trivalent cations. Again, though notwishing to be bound by theory, the monovalent cation-clay product isdifficult to filter and may require isolation by centrifugation, or highdilution and settling tanks. Without washing and removal of monovalention salts, the flocculated clay does not lead tometallocene-support-activator catalysts with sufficient practicalactivity. Furthermore, to the extent that simple ion intercalation, suchas in sodium-exchanged montmorillonite or aluminum-exchangedmontmorillonite, may be evident in the powder XRD of the calcined clayheteroadduct, these materials are thought to be arise as undesirablebyproducts or result from incomplete reaction of the colloidal clay withthe polymetallate.

In another aspect, the colloidal smectite clay can comprise or beselected from colloidal montmorillonite, such as Volclay® HPM-20bentonite. The heterocoagulation reagent can comprise or be selectedfrom aluminum chlorhydrate, polyaluminum chloride, or aluminumsesquichlorohydrate.

According to an aspect, the cationic polymetallate can comprises or beselected from a complex of Formula I or Formula II or any combination ofcomplexes of Formula I or Formula II, according to the followingformulas:

[M(II)_(1-x)M(III)_(x)(OH)₂]A_(x/n).m L   (I)

[LiAl₂(OH)₆]A_(l/n).m L   (II)

wherein:

-   -   M(II) is at least one divalent metal ion;    -   M(III) is at least one trivalent metal ion;    -   A is at least one inorganic anion;    -   L is an organic solvent or water;    -   n is the valence of the inorganic anion A or, in the case of a        plurality of anions A, is their mean valence; and    -   x is a number from 0.1 to 1; and    -   m is a number from 0 to 10.        In this aspect: M(II) can be, for example, zinc, calcium,        strontium, barium, iron, cobalt, nickel, cadmium, manganese,        copper, or magnesium; independently, M(III) can be, for example,        iron, chromium, manganese, bismuth, cerium, or aluminum; A can        be, for example, hydrogencarbonate (bicarbonate), sulfate,        nitrate, nitrite, phosphate, chloride, bromide, fluoride,        hydroxide, or carbonate; n can be, for example, a number from 1        to 3; and L can be, for example, methanol, ethanol or        isopropanol, or water. Further to this aspect, the cationic        polymetallate can be selected from a complex of Formula I,        wherein M(II) is magnesium, M(III) is aluminum, and A can be        carbonate.

In an aspect, the cationic polymetallate can comprises polyaluminumchloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, orpolyaluminum oxyhydroxychloride, or a combination thereof. In a furtheraspect, the cationic polymetallate can include linear, cyclic or clusteraluminum compounds containing, for example, from 2-30 aluminum atoms.The ratio of millimoles (mmol) of aluminum (Al) in the polyaluminumchloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, orpolyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clayin recipe for preparing the smectite heteroadduct can be in a range of,for example, from about 0.75 mmol Al/g clay to about 2.0 mmol Al/g clay,from about 0.8 mmol Al/g clay to about 1.9 mmol Al/g clay, from about1.0 mmol Al/g clay to about 1.8 mmol Al/g clay, from about 1.1 mmol Al/gclay to about 1.8 mmol Al/g clay, or from about 1.1 mmol Al/g clay toabout 1.7 mmol Al/g clay. Alternatively, the millimoles (mmol) ofaluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate,aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride pergrams (g) of colloidal smectite clay in recipe for preparing thesmectite heteroadduct can be, for example, about 0.75 mmol Al/g clay,about 0.8 mmol Al/g clay, about 0.9 mmol Al/g clay, about 1.0 mmol Al/gclay, about 1.1 mmol Al/g clay, about 1.2 mmol Al/g clay, about 1.3 mmolAl/g clay, about 1.4 mmol Al/g clay, about 1.5 mmol Al/g clay, about 1.6mmol Al/g clay, about 1.7 mmol Al/g clay, about 1.8 mmol Al/g clay,about 1.9 mmol Al/g clay, or about 2.0 mmol Al/g clay, including anyranges between any of these ratios or combinations of subrangestherebetween.

In a further aspect, the ratio of millimoles (mmol) of aluminum (Al) inthe polyaluminum chloride, aluminum chlorhydrate, aluminumsesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) ofcolloidal clay in the recipe to prepare the isolated or calcinedsmectite heteroadduct can be about 90% or less, about 80% or less, about70% or less, about 60% or less, about 50% or less, about 45% or less,about 40% or less, or about 35% or less of a comparative ratio ofmillimoles of aluminum to grams of colloidal clay used for thepreparation of a pillared clay using the same colloidal smectite clayand heterocoagulation reagent.

In this aspect, the ratio of aluminum regent to clay in a pillaringrecipe is expressed in mmol Al/g clay, indicating the number ofmillimoles of Al in the aluminum chlorhydrate reagent versus the gramsof clay in the recipe. Specifically, this ratio reflects the ratioemployed in the synthesis recipe, not the ratio in the final pillaredclay product. As an example, considering the Al₁₃-type Keggin ions asdescribed by Ocelli, Clay and Clay Minerals, 2000, 48(2), 304-308, theamount of Al used in the pillared clay preparation is far in excess ofthe amount of Al that eventually is intercalated between the layers inthe final pillared clay solid. The use of an excess of aluminum reagentis employed to provide a maximum of pillar content in the final productand obtain the desired porosity and surface area of the final calcinedmaterial. Kooli in Microporous and Mesoporous Materials; 2013, 167,228-236 discloses that generally, about 6 mmol Al/gram of clay is neededin the recipe in order to optimize pillaring. In a more recent scale-upstudy and optimization of Al₁₃ Keggin ion-pillared clay, Pergher andBertella in Materials, 2017, 10, 712, disclose that 15 mmol Al/g clayand dilute dispersions of about 1 wt. % clay are required for obtainingpillaring with the desired basal spacing and surface areas.

E. Preparation and Properties of the Clay Heteroadduct (HeterocoagulatedClay)

Unlike the pillared clays, the heterocoagulated clay of this disclosureare amorphous solids. Therefore, the preparation of the heterocoagulatedclay provides a three-dimensional structure, but one which is anon-pillared and non-crystalline and amorphous. While not intending tobe bound by theory, it is believed that the regular crystallinestructure of the starting smectite is not simply expanded upon contactwith the cationic polymetallates as described, but rather disrupted uponpreparation of the clay heteroadducts to provide a non-crystalline,non-regular, non-layered amorphous material. Factors which can affectformation of an amorphous three-dimensional structure include reactiontime, reaction temperature, purity of the starting clay and clayparticle size, method of drying, and the like, which are readilydeterminable as described herein for each heterocoagulation reagent andclay system.

In the preparation of the clay heteroadduct, the heterocoagulation agentmay be added to a slurry of the colloidal clay, the colloidal clay maybe added to a slurry or solution of the heterocoagulation agent, or theheterocoagulation agent and colloidal clay may be added to a liquidcarrier at the same time or during an overlapping time period.Alternatively, the heterocoagulation agent and colloidal clay may beadded simultaneously to a heel of heteroadduct product, such as addingthe heterocoagulation agent and clay as either a solid or a suspension,to a vessel or reactor containing water or a water-containing heel.

In an aspect, the liquid carrier in which the clay heteroadduct isprepared can be water or water-based, in which additional components canbe added, such as an alcohol and/or at least one surfactant. Suitablesurfactants can include anionic surfactants, cationic surfactants, ornon-ionic surfactants. Specific examples of liquid carriers or“diluents” and specific examples of surfactants are provided in theAspects of the Disclosure section.

As described, the ratio of heterocoagulation reagent to clay to be usedin the recipe is defined as a ratio that affords a coagulated productmixture such as a slurry having a zeta potential in a range of fromabout positive (+)25 mV (millivolts) to about negative (−)25 mV.Therefore, the amount of heterocoagulation reagent added to a knownsample of clay, that is, the ratio of cationic polymetallate(heterocoagulation reagent) to clay, is determined by titrating the claywith the heterocoagulation reagent. For example, when theheterocoagulation reagent comprises a cationic polymetallate ofaluminum, the ratio of heterocoagulation reagent to clay can be reportedin millimoles (mmol) of aluminum (Al) in the cationic aluminumpolymetallate to grams (g) of clay. The actual amount of cationicpolymetallate used in the formation of the clay heteroadduct, that is,the ratio of heterocoagulation reagent to clay may depend upon factorssuch as the degree of positive charge of the cationic polymetallate, thezeta potential of the clay, and the like. The heterocoagulation reagentand the clay are combined in a ratio such that the resulting slurry(dispersion) of the heterocoagulated clay which forms exhibits a zetapotential in a range of from about +25 mV to about −25 mV.Alternatively, the heterocoagulation reagent and the clay are combinedin a ratio such that the resulting dispersion of the heterocoagulatedclay which forms exhibits a zeta potential in a range of from about +22mV to about −22 mV, from about +20 mV to about −20 mV, from about +18 mVto about −18 mV, from about +15 mV to about −15 mV, from about +10 mV toabout −10 mV, from about +5 mV to about −5 mV, or about 0 mV.

As described in the Examples, a Colloidal Dynamic Zetaprobe Analyzer™was used for zeta potential measurements, including to dynamically trackthe evolving zeta potential during titrations of colloidal claydispersions with cationic polymetallate titrants. Exemplary results froma zeta potential titration are illustrated in the Figures and describedin the Examples, and data are presented for example in Table 4 throughTable 6. For example, FIG. 3 plots the zeta potentials of a series ofdispersions formed during the titration of Volclay® HPM-20montmorillonite with aluminum chlorhydrate (ACH), plotting thecumulative titrant volume of the aqueous ACH solution added (x) versuszeta potential (mV, (y)) of the dispersion. Similarly, FIG. 4 plots thecumulative mmol Al/g clay versus zeta potential (mV) of the dispersionfor the same titration. Samples of some of the solid products formedduring this zeta potential titration of HPM-20 clay with ACH werecollected, and FIG. 2 provides a powder XRD pattern of this series ofcalcined products collected from during this zeta potential titration ofHPM-20 clay with ACH. As a result, the comparison and correlation of themmol Al/g clay with the zeta potential and the filterability of theresulting products were examined, and from this analysis, it wasunexpectedly discovered that when the clay and the heterocoagulationreagent comprising at least one cationic polymetallate were contacted ina liquid carrier in an amount or ratio that provides a slurry of thesmectite heteroadduct having a zeta potential in a range of from aboutpositive 25 mV (millivolts) to about negative 25 mV, the resultingproduct was readily filterable, could be used as a support-activatorwithout washing or with minimal washing, and imparted highpolymerization activity to the supported metallocene catalysts.

In synthetic reactions or titrations using a cationic polymetallate,calculating the ratio of the number of millimoles of metal atoms in thepolymetallate per mass of clay provides a useful metric for comparisonsacross polymetallates. For example, in the zeta potential titrationsusing an aluminum cationic polymetallate as the heterocoagulationreagent, the ratio of the number of millimoles of aluminum per clay massas shown in the FIG. 4 titration curve allows a more direct comparisonof differing Al-containing heterocoagulation reagents. The derivation ofthis value is performed by obtaining the aluminum weight percent of theheterocoagulation agent, which is typically provided from themanufacturer either directly, or as an aluminum oxide (e.g. Al₂O₃)equivalent weight percent. In the latter case, the aluminum weightpercent can be derived from multiplying the aluminum oxide weightpercent by the weight proportion of aluminum in the empirical formula.From this aluminum weight percent, the molar amount of aluminumheterocoagulation reagent can be determined, and the molar aluminum/claymass ratio can be obtained.

For example, FIG. 4 illustrates that one ratio of aluminum chlorohydrate(ACH) to Volclay® HPM-20 expressed in mmol Al/g of clay that fallswithin the desired zeta potential range is 1.76 mmol Al/g clay. Theactual ratio may vary slightly depending on the lot, method ofpreparation, contamination or age of the aluminum chlorhydrate, and orthe particular batch of Volclay® HPM-20. FIG. 2 presents the zetapotential titration of Volclay® HPM-20 from American Colloid Companywith 22 wt. % aluminum chlorhydrate from GEO Specialty Chemicals. Themmol Al/g clay can thus be determined as the point at which the zetapotential of colloidal species in the mixture falls below +25 mV andabove −25 mV, for example, between about +10 mV and −10 mV, providing aheterocoagulated solid that is readily isolated by conventional methodsof filtration such as using filter paper, as described in detailhereinbelow. Thus, ready filtration of the resulting clay heteroadductcan be carried out with or without vacuum assistance, a belt filter, andthe like.

The resulting dispersion of the heterocoagulated clay which formsexhibits a zeta potential in the disclosed range centered about zero,provides the readily isolable (readily filterable) heteroadduct. Whilenot restricting the ranges of zeta potentials disclosed and claimedherein, and not wishing to be theory bound, when the amount ofheterocoagulation reagent combined with the colloidal smectite (such asthe dioctahedral smectites described herein) provides a particledispersion of near zero zeta potential, such that the particles in thedispersion have little or no electrophoretic mobility, excellent yieldand filterability of the clay heteroadduct can be obtained. This zerozeta potential point may be considered a nominal target ratio ofcationic polymetallate to colloidal clay. Aspects of electrophoreticmobility are described in, for example, Gu, et al., Clay and clayminerals, 1990, 38(5), 493-500.

The experimentally derived ratio of heterocoagulation reagent (cationicpolymetallate) to colloidal clay can be determined by providing adispersion of the colloidal clay in water, adding the dispersion to azeta potential measurement vessel, and measuring the initial zetapotential of the clay dispersion. A solution of the selectedheterocoagulation agent is prepared and added to the dispersion inportions, with the zeta potential of the dispersion being measured aftereach addition. The ratio of cationic polymetallate to colloidal clayused to prepare the easily filterable clay heteroadduct is calculated bydetermining the ratio of heterocoagulation reagent needed to achievezero or essentially zero zeta potential from the resultant zetapotential titration curve.

In a further aspect, when the zeta potential titration curve is not welldefined or is discontinuous at or near zero potential (mV),extrapolation of the points closest to zero zeta potential may be usedto estimate the crossover point at which the zeta potential curvecrosses from a negative zeta potential to a positive zeta potential,thus describing the nominal target ratio. In another aspect, when thezeta potential titration curve is discontinuous near zero, and remainsdiscontinuous at or near the bounds of zeta potential (for example, ±20mV or ±25 mV), linear extrapolation between the points on the titrationcurve directly before and after the discontinuity may be used toestimate the heterocoagulation reagent to clay ratio useful to achievethe desired zeta potential. Examples of zeta probe (zeta potential)titrations and determinations of the nominal target ratios ofheterocoagulation reagent to clay are provide in the figures andExamples section of the disclosure. For example, see FIG. 2 through FIG.8, Example 8 through Example 12, and Example 38.

The ratio of mmol of aluminum (mmol Al) of aluminum chlorohydrate tograms of Volclay® HPM-20 colloidal montmorillonite used to prepare theclay heteroadducts can be significantly less, sometimes over an order ofmagnitude less, than the ratio of mmol Al/g clay used to preparepillared HPM-20 clay with aluminum chlorohydrate. That is, using thesame cationic polymetallate and colloidal clay, but using a mmol Al/gclay ratio which exceeds the range dictated by the zeta potential fromabout +25 mV to about −25 mV for the clay heteroadduct dispersion,pillared clays will form. Therefore, the ratio of cationic polymetallateto colloidal clay to form the clay heteroadducts of the presentdisclosure differs from that used in, for example, U.S. Patent Appl.Publication No. 2018/0142047 and 2018/0142048 to W. R. Grace, whichemploy lanthanide containing-Al-pillared clays as support-activators.

Conversely, when too low a ratio of heterocoagulation reagent to clay isused in the recipe in an attempt to make a clay heteroadduct, the readyfiltration of the resulting contact product by conventional filtrationmeans is not possible. This feature is illustrated in Example 19, wherea recipe for 0.30 mmol Al/g clay using aluminum chlorhydrate (ACH) andHPM-20 clay to prepare the clay heteroadduct would, when derived fromthe zeta potential titration in FIG. 2, predict a zeta potential of −44mV. Filtration of the resulting contact product was difficult andisolation and preparation of the sample required centrifugation toisolate the product. Products such as these may be referred to herein asa “heteroadduct” for convenience even though outside the zeta potentialrange for ready filterability. Similarly, in Example 26 where using arecipe for 0.30 mmol Al/g clay using powdered ALOXICOLL® 51P aluminumchlorhydrate (Parchem Fine and Specialty Chemicals) provided a contactproduct heteroadduct which was difficult to process and isolate, andcentrifugation was required to isolate product.

The starting clay particles such as montmorillonite carry a permanentnegative charge due to isomorphous substitution of ions into one of the“TOT” layers, for example, substitution of Mg²⁺ for Al³⁺ in theoctahedral alumina layer which imparts a negative charge. Therefore, thestarting clay forms a dispersion or suspension in water as thenegatively-charged clay particles repel each other and are stabilized inthe polar aqueous environment. Though not wishing to be bound by theory,the contact of cations such as the cationic polymetallates disclosedherein with the negatively-charged colloidal clays is thought toinitially promote coagulation of the colloidal clay, through coulombicattraction of opposite charges and neutralization of the clay surfaces.This neutralization results in precipitation of the clay heteroadductfrom the polar aqueous carrier as large agglomerated or coagulatedparticles which are readily filterable. As additional cationicpolymetallate is added in excess to the coagulate composition, such aswhen preparing ion-exchanged, protic acid treated or pillared clays,some or all of the agglomerated surface may be “re-charged” aspositively-charged species, and thereby become re-suspended in a polarcarrier such as water. This re-suspension provides a dispersion ofhighly-charged species which are difficult-to-impossible to filter offand which plug the filter media. The clay heteroadducts of thisdisclosure are formed below these high ratios and thereby thought toavoid the re-charging and re-suspension of the clay heteroadduct. Thus,the near zero zeta potential surface of the clay heteroadducts providesa readily filterable product and coincidentally substantially avoidspillaring of the clays, and further avoids the uniformly intercalatedclay structures of the pillared clay and of the starting clay.Surprisingly, even without pillaring, these structures, form thermallystabile, robust structures which can serve as very activesupport-activators for metallocenes.

In an aspect, FIG. 1 provides a schematic summary of the practical anddesirable aspects of preparing neutral or weakly charged dispersionswith a low magnitude, near zero, or zero zeta potential. Filtration ofclay heteroadducts with these properties proceeds rapidly, and typicallyfew sequential filtrations are required in order to generate a supportwith desirable surface area, porosity, and polymerization activity. Incontrast, highly charged dispersions, like the type obtained from thepreparation of pillared clays, are not readily filterable and must beprocessed using relatively more expensive and cumbersome methods toobtain a useful support-activator.

Also in contrast to other materials such as those described by Jensen etal. in U.S. Patent Appl. Publication Nos. 2018/0142047 and 2018/0142048assigned to W. R. Grace, the clay heteroadduct of the presentdisclosure, after filtration and calcination at 300° C. or higher, canexhibit no, or substantially no d001 peak of 2 theta (2θ) less than 10degrees in the powder XRD scan. This feature is illustrated in theexamples of FIG. 2 which present the powder XRD (x-ray diffraction)patterns of a series of calcined products from combining aluminumchlorhydrate (ACH) and Volclay® HPM-20 montmorillonite, each samplediffering by the amount of cationic polymetallate used to prepare theheterocoagulated clay. These samples were prepared according to theExamples 18, 20-21, 23 and 25, except as follows. The sample marked asderived from 6.4 mmol Al/g clay sample (top) represents a typicalpreparation of Al₁₃-pillared clay (see Example 5). The XRD of thestarting clay itself (bottom) is marked as derived from 0 mmol Al/g claysample (see Example 3).

Referring again to FIG. 2 and the Examples for the preparation of thesesamples, Example 12 through Example 30 provide the preparative methodsfor the formation of ACH-clay heteroadducts from 0 mmol Al/g clay to 6.4mmol Al/g clay examined in this figure, including some comparativeExamples. As the XRD patterns below about 10 degrees 2θ shown in FIG. 2illustrate, there are two main peak changes as the proportion ofcationic polymetallate is increased in the preparative recipe. Firstly,an XRD peak at about 9 degrees 2 theta (2θ) corresponding to thestarting clay disappears, and a peak from about 9 degrees (2θ) to about10 degrees (2θ) gradually grows in as the proportion of cationicpolymetallate is increased. The disappearance of the 9 degrees (2θ) peakappears to indicate the course of the reaction to form theheterocoagulated clay which is largely amorphous, and the subsequent9-10 degrees (2θ) peak likely represents simple ion intercalation, suchas Al³⁺ ion intercalation, characterized by a smaller basal spacing thanthe initial ion exchanged clay. As even more polymetallate is added tothe slurry, a peak grows in from about 4 degrees (2θ) to about 6 degrees(2θ), and tis peak represents the major product at 6.4 mmol Al/g clay.This 4-6 degrees (2θ) peak likely corresponds to the Kegginion-intercalated pillared structure which forms as the concentration ofadded polymetallate increases. At the clay concentration of theseexperiments, which is not highly diluted (that is, not less than 1 wt. %clay), the 6.4 mmol Al/g clay product could not easily be isolated withsimple filtration and instead had to be isolated and washed usingmultiple centrifugation and decanting steps. In addition, the startingclay colloidal clay as a comparative sample also could not be readilyfiltered.

In one aspect, when aluminum chlorhydrate (ACH) is the heterocoagulationreagent and Volclay® HPM-20 montmorillonite is the colloidal clay, thezeta potential data and XRD data indicated that the range of zetapotential of ±25 mV corresponds to a range of approximately 1 mmol Al/gclay to 1.8 mmol Al/g clay. Similarly, the range of zeta potential of±15 mV in which the clay heteroadduct is less charged corresponds to arange of approximately 1.3 mmol Al/g clay to 1.7 mmol Al/g clay. Thesedata also indicated that the zeta potential of 0 (zero) mV in which theclay heteroadduct is near zero charge corresponds to approximately 1.5mmol Al/g clay. FIG. 2 demonstrates that, at 1.52 mmol Al/g clay, thepowder XRD indicates little or virtually no pillaring (XRD patternbetween 4.8 degrees (2θ) to 5.2 degrees (2θ)) and little or virtually nosimple ion exchanged clay (XRD pattern between 9 degrees (2θ) and 10degrees (2θ)) relative to the mineral impurities that exist in thestarting colloidal clay in the range of 2 theta between 20-30 degrees2θ.

Thought not wishing to be bound by theory, when using aluminumchlorhydrate and colloidal smectite, the near zero charge of theheteroadduct provided by the 1.5 mmol Al/g clay recipe corresponds toless than about half of the amount (ratio) of aluminum that may beactually incorporated into an Al₁₃-pillared smectite, and a much smallerfraction of the aluminum that is used in pillaring recipes. See, forexample, Schoonheydt et al., Clay and Clay Minerals 1994, 42(5),518-525, which describes this amount as approximately 3-4 mmol Al/g claythat is actually incorporated. As described above, the amount ofheterocoagulation reagent that provides the zeta potential of 0 (zero)mV heteroadduct, which may be considered a preferred amount of about 1.5mmol Al/g clay, is an order of magnitude less than the amount used foroptimized pillaring recipes of 15 mmol Al/g clay. It was surprisinglydiscovered that the clay heteroadduct of this disclosure ischaracterized by the absence or substantial absence of a regularlyintercalated, pillared structure, and yet the clay heteroadduct providescomparable and often greater activity as a metallocene support-activatorthan the pillared clays.

The clay heteroadduct of this disclosure is not the regularlyintercalated, pillared structure such as described by Jensen et al. inU.S. Patent Appl. Publication Nos. 2018/0142047 and 2018/0142048.Specifically, the clay heteroadducts of this disclosure are not or aresubstantially not regularly complex-ion intercalated (“not regularlyintercalated”), microporous catalytic components comprising layered,colloidal clay having a multiplicity of pillars interposed between theexpanded molecular layers of the clay. Therefore, the clay heteroadductsof this disclosure are not regularly ordered, and there is no evidenceof the consistent regularity imparted by consistent pillars and/orconsistent intercalated layers of aluminum oxides or hydroxides, such asderived from an Al₁₃ Keggin ion or a lanthanide-centered poly-Al₁₃pillar as in U.S. Patent Appl. Publication Nos. 2018/0142047 and2018/0142048. However, especially in some examples that were multiplywashed and filtered, powder XRD peaks indicative of some pillaring canbe detected. For example, the XRD pattern of the 1.76 mmol Al/g claysample corresponds approximately to a +23 mV zeta potential, but theintensity of the peak is substantially less than that of pillaring-typerecipes, for example, using 6.4 mmol Al/g clay and greater.

Thus, in a further aspect, the calcined clay heteroadduct of thisdisclosure is absent the ordered domains as evidenced by the lack of XRDpeaks between 0-12 degrees 2θ. This observation highlights onedifference from the simple monoatomic ion exchange process or thecomplex polyatomic ion exchange processes by which sodium ions (forexample, in a starting sodium montmorillonite) are exchanged fordivalent, trivalent or multivalent ions which afford after drying,ordered and layered structures reflecting the size of the simplemonoatomic ion or the size of the polyatomic ion such as the Al₁₃ Kegginion, or other pillared species as evidenced by the associated d001 basalspacing in the XRD.

In one aspect, the isolated clay heteroadducts are collected, forexample by filtration, and they are not washed. In another aspect, theisolated clay heteroadducts are minimally washed, for example one timeor two times with an appropriate washing liquid such as water, forexample, just sufficient to provide some purification benefit. Thoughnot wishing to be bound by theory, as described for example bySchoonheydt et al., Clay and Clay Minerals 1994, 42(5), 518-525, whichis incorporated herein by reference, washing has been observed tofacilitate pillaring. Therefore, washing to the extent that pillaringoccurs appears to sacrifice the isolated desirable clay heteroadduct toform the undesired by-product pillared clay.

In another aspect of the disclosure and in further contrast withregularly intercalated, ion-exchanged clays such as those disclosed inJensen et al. in U.S. Patent Appl. Publication Nos. 2018/0142047 and2018/0142048, extensive washing of the solid clay heteroadduct of thisdisclosure until the wash water exhibits a negative AgNO₃ test (chloridetest) is obtained is not necessary to impart high polymerizationactivity to the clay heteroadduct. In contrast, and without employingdilute solutions, a single filtration of immediate heteroadduct mixturescontaining approximately 5 wt. % solids provides good polymerizationactivity in the final catalyst mixture. This feature is demonstrated,for example, in Examples 22, 24, 29-31, 33 and 35-36. For example, thedifference in the preparation of the ACH-clay heteroadduct betweenExample 22 and Example 23 is whether the preparation of the productemployed one filtration versus two filtrations, the later including asingle wash between each filtration. Thus, in the Example 22 preparationof a clay heteroadduct employing a single filtration, the filtrateobtained from filtering the slurry was characterized by a conductivityof 1988 μS/cm. In contrast, the Example 23 preparation of a clayheteroadduct employing two filtrations with a wash between provided afiltrate which was characterized by a conductivity of 87 μS/cm, adifference of almost 23-fold. Yet the polymerization activities ofcatalysts prepared using these support-activators varied by only 10%,which the skilled person would recognize as within the range ofvariability bench-scale polymerization tests.

Similarly, the polymerization runs using the Example 24 versus Example25 support-activators further point to the economically-beneficialaspects of the support-activators, where a single filtration of the clayheteroadduct versus two filtrations again affords essentially the samepolymerization activity. Specifically, the catalyst formed from thesingle filtration support-activator exhibited an activity of 3581 g/g/hversus 3547 g/g/h observed for the catalyst formed from the doublefiltration support-activator. The conductivity of the slurry of thesingle filtration product (Example 24) had a conductivity of 1500 μS/cmand the final slurry of the double filtration product (Example 25) had aconductivity of 180 μS/cm. Therefore, it was unexpectedly discoveredthat extensive washing of the clay heteroadduct is not necessary forgood polymerization activity (again in contrast to U.S. Patent Appl.Publication Nos. 2018/0142047 and 2018/0142048).

The samples produced using 1.52 mmol Al/g clay according to Example 28(additional washing step) and Example 29 (single filtration) providedcatalyst activities of 1404 g/g/h and 1513 g/g/h, respectively. In thiscomparison, the single filtration heteroadduct slurry of Example 29having a conductivity of 1750 μS/cm actually provided a higher activitythan the Example 28 sample which was washed and filtered twice after theinitial filtration and having a slurry conductivity of 169 μS/cm. Inanother aspect and in further contrast to the support-activators of U.S.Patent Appl. Publication Nos. 2018/0142047 and 2018/0142048, it is notnecessary to age the clay heteroadduct slurry of this disclosure for atleast 10 days at room temperature or at elevated temperatures prior toisolation and use. Rather, the clay heteroadduct slurry of thisdisclosure can be immediately filtered and then dried or calcined, thusproviding a far more efficient synthesis of the support-activator.

Formation of the heterocoagulation agent has not been found to be verytemperature sensitive, in that the clay forms a heteroadduct with theheterocoagulation agent over a wide range of temperatures. For example,formation of the clay heteroadduct proceeds in a range of from about 20°C. to about 30° C., although temperatures ranging from almost 0° C. tothe boiling point of the slurry containing the clay heteroadduct can beused.

The pH of the solution containing the heterocoagulation agent can beadjusted to provide for minimum zeta potential of the heterocoagulatedproduct, which can be readily determined through experimentation asdescribed by Goldberg, et al., Clay and Clay Minerals, 1987, 35,220-270. The resulting heteroadducts isolated by this method also can beused with metallocenes for olefin polymerization. Further, this methodto adjust the zeta potential may be used in such cases where the ratioof heterocoagulation agent to clay does not itself afford a zetapotential between and including the ±25 mV (or alternatively, ±22 mV,±20 mV, and the like) range disclosed herein. However, this pHadjustment method requires an additional step in the synthesis andisolation of the clay heteroadduct, and it has been observed that thismethod does not guarantee ready filterability or optimum finalpolymerization activity. Though not wishing to be bound by theory, it isbelieved that pH adjustment in such cases can lead to protonated orhydroxylated clays, heterocoagulation reagents, and/or clayheteroadducts, which can affect the properties and ultimate catalyticactivity of the clay heteroadduct.

In another aspect, this disclosure provides for the removal of salts andminor amounts of non-coagulated, colloidal materials formed in thepreparation of the heterocoagulated product. For example, solubleby-products, such as sodium chloride and the like, in addition to minoramounts of colloidal materials, are readily removed from theheterocoagulated product by washing with water followed by simplefiltration of the heterocoagulated product. Washing can be accomplishedby re-suspension of the isolated heterocoagulated product into water, bymechanical stirring or shaking to form a slurry, which can then bere-filtered. This method contrasts the pillaring processes thatgenerally requires multiple washing and isolations steps using highspeed centrifugation, decantation, changing pH of the pillaringagent-clay solution, or large dilution and settling tanks for isolationof the pillared clay product. Such additional steps add time and cost tothe separating and washing a pillared or chemically-treated clay mineraladduct from impurities such as its starting components, nano- ormicro-sized quartz, and other inorganic metal oxides. Conversely,filtration of the clay heteroadduct may be conducted batchwise throughsintered glass frit, metal frit, common filter paper, felt or otherfiltration media, or continuously filtered using a moving belt filter.Filtration is practical because it is fast, for example, filtration canbe completed in as little as one minute or even less, less than or equalto about 5 minutes, less than or equal to about 10 minutes, less than orequal to about 15 minutes, less than or equal to about 30 minutes, lessthan or equal to about 1 hour, less than or equal to about 2 hours, lessthan or equal to about 5 hours, less than or equal to about 8 hours, orless than or equal to about 24 hours.

The conductivity of the filtrate or slurry of the clay heteroadduct canbe monitored using a commercially available conductance meter. In anaspect, when the concentration of the slurry is in a range of from about1 wt. % to about 10 wt. % solids, from about 2.5 wt. % to about 10 wt. %solids, or from about 5 wt. % to about 10 wt. % solids, the clayheteroadduct slurry can be characterized by a conductivity in a range offrom about 100 μS/cm (0.1 mS/cm) to about 50,000 μS/cm (50 mS/cm), fromabout 250 μS/cm to about 25,000 μS/cm, or from about 500 μS/cm to about15,000 μS/cm, or alternatively from about 1,000 μS/cm (1 mS/cm) to about10,000 μS/cm (10 mS/cm).

The heterocoagulated solid may be dried via azeotropic methods ifdesired, as carried out in some of the Examples. Azeotropic drying isbelieved to preserve pore volume and surface area during drying ascompared to simply heating the heterocoagulated solid. For example, thefiltered smectite heteroadduct may be re-suspended in a slurry with asolvent that will reduce the boiling point of water present in theheterocoagulated product. This water lost during drying may becharacterized as free water or chemically-bound water. That is, waterlost during drying can derive from free water which is located in theheteroadduct pores or on the external surface and chemically-bound waterwhich is generated from dehydrating surface hydroxyls during the dryingand calcining process. Various alcohols are useful as azeotroping agentsincluding, but not limited to, 1-butanol, 1-hexanol, isopentanol,ethanol and the like, including any combinations thereof.

Freeze-drying, flash-drying, fluidized bed drying, or any combinationthereof also can be used to remove water from the clay heteroadduct.These methods whether used alone or in combination during the removal ofwater may help to preserve pore volume and surface area during thedrying process. In another aspect, spray drying of a suspension of theclay heteroadduct can be employed to control support-activator andsupported catalyst particle morphology. For example, suspensions of theclay heteroadduct in aqueous solvent or organic solvents or incombinations of aqueous and organic solvents can be spray dried. Dry orwet milling and sieving may be employed to refine the heterocoagulatedclay morphology, size and size distribution. These methods can beemployed individually or in combination in order to achieve the desiredsupport-activator particle morphology, particle size and particle sizedistribution of the clay-heteroadduct. Spray drying and/or sieving ofthe clay heteroadduct can be used, as can other methods known to thosein the art for removing fines or larger particles that can beproblematic in conveying or using the heteroadduct as asupport-activator.

The heterocoagulated solid can be calcined or heated in a fluidized bed,for example, temperatures in a range of from about 100° C. to about 900°C. For example, the heterocoagulated smectite clay can be calcined orheated in a fluidized bed at temperatures ranging from about 100° C. toabout 900° C., from about 200° C. to about 800° C., from about 250° C.to about 600° C., or from about 300° C. to about 500° C. Calcining canbe conducted in the ambient atmosphere (air), for example, calcining canbe carried out in dry air at temperature in a range of at least 110° C.,for example, the temperature can be in a range of from about 200° C. toabout 800° C., and for a time in the range of about 1 minute to about100 hours. For example, the smectite heteroadduct can be calcined usingany one of the following conditions: a) a temperature ranging from about110° C. to about 600° C. and for a time period ranging from about 1 hourto about 10 hours; b) a temperature ranging from about 150° C. to about500° C. and for a time period ranging from about 1.5 hours to about 8hours; or c) a temperature ranging from about 200° C. to about 450° C.and for a time period ranging from about 2 hours to about 7 hours.

The clay heteroadduct may also be calcined at temperatures from about225° C. to about 700° C. for a period of time in a range of about 1 hourto about 10 hours, most preferably, temperatures from about 250° C. toabout 500° C. and a time in a range of about 1 hour to about 10 hours.Alternatively, calcining in air can be carried out at temperatures in arange of from 200° C. to 750° C., from 225° C. to 700° C., from 250° C.to 650° C., from 225° C. to 600° C., from 250° C. to 500° C., from 225°C. to 450° C., or from 200° C. to 400° C. As indicated, a calciningtemperature selected from any single temperature or range of twotemperatures, for example, temperatures separated by at least 10° C.(that is 10 Centigrade degrees) in the range of 110° C. to 800° C. canbe used for developing final catalytic activity.

Thermal treatment such as calcining can be conducted in ambientatmosphere or under other such conditions which facilitate the removalof water, for example, calcining may be carried out in a carbon monoxideatmosphere. Use of such atmospheres may remove surface hydroxyls moreefficiently at lower temperatures as compared to the temperatures usedin an ambient air calcining process, thus preserving greater pore volumeand surface area during dehydration of the surface. After calcining, theheterocoagulated product may be described as a continuous,non-crystalline combination of clay and inorganic oxide particles, whichwe refer to herein as an activator-support or support-activator.

The determination of the total porosities, pore volume distributions,and surface areas of the activator supports of this disclosure can beachieved through any method known in the art, for example, an analysisusing nitrogen gas adsorption-desorption measurements. The adsorptionisotherm or desorption isotherm plots the volume of gas (in this case,nitrogen) that either adsorbs onto, or desorbs from, the surface of ananalyte (clay heteroadduct) as pressure is either increased ordecreased, respectively, at a constant temperature. Isotherm data can beanalyzed using the BJH method to determine total pore volume andgenerate a pore size distribution as described below, and isotherm datacan be analyzed using the BET method to determine surface area.

Heterocoagulation of the smectite clay can provide activator supportsthat have substantial porosity and exhibit catalyst activationproperties when combined with metallocenes or other organotransitionmetal compounds capable of polymerizing olefins. In one aspect, thecalcined clay heteroadduct can exhibit a BJH porosity in a range of fromabout 0.2 cc/g to about 3.0 cc/g, from about 0.3 cc/g to about 2.5 cc/g,or from about 0.5 cc/g to about 1.8 cc/g. The calcined clay heteroadductcan also exhibit a BJH porosity of greater than or equal to 0.5 cc/g.Calcined clay heteroadducts having a porosity as low as about 0.2 cc/gcan be used, for example, heteroadducts exhibiting a BJH porosity in arange of from about 0.2 cc/g to about 0.5 cc/g, but clay heteroadductshaving a porosity of less than about 0.2 cc/g can exhibit lowerpolymerization activity, for example, <200 g PE/g support-activator/hr,when combined with metallocenes such asbis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride) to make thecatalyst system. In this disclosure, the term “g support-activator”refers to the grams of the calcined clay heteroadduct used to make thecatalyst.

A comparison of the BJH porosities of clays and clay heteroadduct ispresented in FIG. 10, FIG. 11, and FIG. 12. The BJH pore volume analysisof the starting montmorillonite which was calcined but otherwisenon-azeotroped and untreated with a heterocoagulation agent is presentedin FIG. 11 (Example 1). The pore volume analysis of the startingmontmorillonite which was sheared, then azeotroped and calcined, butotherwise untreated with a heterocoagulation agent is presented in FIG.12 (Example 3). Finally, the pore volume analysis of the aluminumchlorhydrate (ACH) heterocoagulated clay of Example 18 (1.76 mmol Al/gclay) is presented in FIG. 10. Thus, in the absence of aheterocoagulation reagent, calcined smectites such as bentonites canpossess BJH porosities from about 0 cc/g to about 0.2 cc/g.

Cumulative pore volume between specific pore diameter bounds can bedetermined using the BJH method derived pore volume distribution. Thecumulative pore volume between pore diameters of X nm (nanometers) and Ynm (V_(X-Y nm)), in which X nm is the lower bound of pore diameter, andY is the upper bound of the pore diameter, is determined by subtractingfrom the total cumulative pore volume from pore diameters 0 nm to Y nmby the total cumulative pore volume from pore diameters 0 nm to X nm. Insituations where the total cumulative pore volume for either the upperbound or lower bound of pore diameter is not available, this pore volumeis estimated by linear interpolation between the two closest porediameter points for which cumulative pore volume data is available.

In one aspect of the calcined clay heteroadduct, the combined orcumulative pore volume of pores between 3-10 nm diameter (V_(3-10 nm),or “small mesopores”) can comprise less than 55% of the cumulative porevolume of pores between 3-30 nm (V_(3-30 nm)). In a further aspect,V_(3-10 nm) can comprise less than 50% of the cumulative pore volumeV_(3-30 nm), or alternatively, V_(3-10 nm) can comprise less than 40% ofthe cumulative pore volume V_(3-30 nm). This feature is illustrated bythe data of FIG. 10, which sets out the BJH pore volume analysis ofExample 18 smectite heteroadduct, in which the value of V_(3-10 nm) isabout 0.33 (V_(3-30 nm)). This pore volume analysis contrasts with BJHpore volume analysis of both the untreated, non-azeotroped clay (Example1, FIG. 11) and those of the azeotroped clay (Example 3, FIG. 12), bothof which are characterized by V_(3-10 nm) being greater than 0.55(V_(3-30 nm)).

These pore volume features of the clay heteroadduct of FIG. 10 of thisdisclosure contrast with the pore volume features of the acid-treatedclays of Murase et al. in U.S. Pat. No. 9,751,961, which discloses thatthe sum of the volumes of pores having a diameter from 2 nm to 10 nm(V_(2-10 nm)) accounts for 60% to 100% of the total volume of mesopores,that is, all pores from 2 nm to 50 nm. (See, FIG. 1 and Table 1 of U.S.Pat. No. 9,751,961). Specifically, Murase et al. discloses that thesmaller mesopores from 2 nm to 10 nm make up the majority of the totalmesopore volume (2 nm to 50 nm), where the total mesopore volume can becalculated, for example, by V_(2-10 nm)+V_(10-30 nm)+V_(30-50 nm). Incontrast, the clay heteroadducts of this disclosure are characterized bythe volume of the smaller mesopores V_(3-10 nm) that is exceeded byV_(10-30 nm) alone. While not wishing to be bound by theory, it isthought that the increased proportion of larger mesopores as a share ofthe total porosity in this disclosure facilitates diffusion andaccessibility of the metallocene compound to the ionizing site on clayheteroadduct surface. This is thought to contrast with the smallermesopores which may hinder or even preclude diffusion of the metalloceneto surfaces containing the ionizing sites, particularly for metalloceneswith a radius of gyration that exceeds the smallest end of the mesoporediameter.

Additionally, as shown for example by Uchino et al. in U.S. Pat. No.6,677,411, pore size distributions determined by the BJH method may bedepicted by plotting dV(log D) vs. pore diameter. The diameter showingthe highest value of this function can be represented by the term D_(M)and is considered the most frequently appearing pore diameter. That is,D_(M) is the diameter corresponding to the point with the highest valueof DV(log D) in the region between 30 Å and 500 Å pore diameter. Theordinate value of D_(M), which is the maximum value, is represented bythe term D_(VM). In one aspect, this logarithmic differential porevolume distribution typically possesses a local maximum between about 30Å and about 40 Å (Angstroms). This local maximum intensity also may bethe global maximum D_(VM). In an aspect, the intensity at D_(VM) can beat most about 200% of the intensity of the maximum value of dV(log D)between 200 Å and 500 Å. Alternatively, the intensity at D_(VM) can beat most about 120% of the intensity of the maximum value of dV(log D)between 200 Å and 500 Å. Alternatively, still, the intensity at D_(VM)can be at most about 100% of the intensity of the maximum value ofdV(log D) between 200 Å and 500 Å. In another aspect, the maximum valueof dV(log D) between 200 Å and 500 Å exceeds all values of dV(log D)between 30 Å and 200 Å. This contrasts to, for example, the acid treatedclays of Uchino et al. in U.S. Pat. No. 6,677,411, which is incorporatedby reference herein, in which the maximum D_(VM) values observed in thelogarithmic differential pore size distributions of the desirableembodiments possess associated diameters D_(M) between 60 Å and 200 Å.

Similarly, the treated clay activators described by Casty et al. in U.S.Pat. No. 7,220,695 define a preferred embodiment in which the diameterD_(M) showing maximum D_(VM) value resides between 60 Å and 200 Å(Angstroms). In contrast, the most frequently appearing pore diameterD_(M) of the clay heteroadducts of this disclosure resides either in therange of from 30 Å to 40 Å or in the range from 200 Å to 500 Å.

Further, the differential logarithmic pore volume distributions in U.S.Pat. No. 6,677,411 demonstrate substantially lower intensities in the200 Å and 500 Å range compared to the 60 Å to 200 Å range. The maximumvalue of dV(log D) in the 200 Å and 500 Å range is typically less than10% that of the maximum value of dV(log D) in the 60 Å and 200 Å range.In contrast, the clay heteroadducts of this disclosure can provide amaximum value of dV(log D) in the 200 Å and 500 Å range, which istypically greater than 100% that of the maximum value of dV(log D) inthe 60 Å and 200 Å range. Though not wishing to be bound by theory, thepresence of a larger share of the bigger mesopores in the clayheteroadducts of this disclosure is thought to be desirable due togreater ease of metallocene diffusion to ionizing sites of thesupport-activator.

F. Filterability of the Smectite Heteroadduct

The clay heteroadducts prepared in slurry form within the zeta potentialrange according to this disclosure unexpectedly exhibited an improvedease of isolation as compared to the analogous pillared clays preparedusing the same smectite clay and heterocoagulation reagent.Specifically, the clay heteroadducts could be readily isolated byfiltration, unlike the pillared clays. This enhanced filterability wasobserved and quantified by, for example, comparing the settling rate ofslurries of a clay heteroadduct versus the settling rate of an analogouspillared clay prepared using the same clay and a slurry containingidentical amounts of the clay.

A slurry settling rate comparison between a pillared clay and aheterocoagulated clay, each prepared with a 5 wt. % aqueous dispersionof HPM-20 clay, is set out in Table 1. Each slurry was prepared asdescribed in the referenced Examples and added to a graduated cylinder,and the settling rate was measured over time by the observed volume ofthe substantially clear layer which is absent the cloudiness of visiblecolloidal particles at the top of the slurry. In this comparison, thesettling rate of the heterocoagulated clay was significantly faster, forexample, 5-fold faster on a volume basis. While not wishing to be boundby theory, it is thought that the increased particle size of theheterocoagulated clay dispersion having a zeta potential in a relativelynarrow range around 0 mV, for example in a range of about ±10 mV, favorsflocculation relative to pillared clay particles, which in contrast tendto remain dispersed.

TABLE 1 Slurry settling rate comparison between a pillared clay and aheterocoagulated clay, each prepared with a 2.5 wt. % aqueous dispersionof HPM-20 clay Support type Settling Settling Example (mmol Al/g clay)volume (mL) time (h) 43 Pillared clay  3 mL 95 h  (5.7 mmol Al/g clay)42 Hetereocoagulated clay 15 mL 95 h (1.52 mmol Al/g clay)

Accordingly, one method by which the filterability of theheterocoagulated clay slurries may be assessed as being “readilyfilterable” is by examining the settling rate of the slurry as comparedwith the settling rate of pillared clay slurries. In one aspect, acomposition such as the clay heteroadduct is readily or easilyfilterable if the settling rate (as explained herein) of a 2.5 wt. % ofthe aqueous heteroadduct slurry is 3 times, 3.5 times, 4 times, 4.5times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times greateror more, than the settling rate of a 2.5 wt. % of the aqueous pillaredclay slurry prepared using the same colloidal smectite clay, the sameheterocoagulation reagent, and the same liquid carrier, wherein thesettling rates are compared at about 12 hours, about 18 hours, about 24hours, about 30 hours, about 36 hours, about 48 hours, about 72 hours,about 95 hours, about 96 hours, or about 100 hours, or more from thestart of the settling test.

An additional demonstration of filterability was observed by quantifyingthe filtration rate or filtration speed of the clay slurries, asillustrated in Table 2. When a pillared clay slurry and aheterocoagulated clay slurry each using 5 g of clay were prepared to atotal mass of 250 g and filtered, the heterocoagulated clay slurryfiltered quickly and the filtrate water rapidly separated, whereas thefiltration speed was over 80% slower for the pillared clay slurry.Again, while not wishing to be bound by theory, it is thought that theincreased particle size of the flocculated heterocoagulated clay allowsfacile separation of the heterocoagulated clay particles and water,whereas the smaller particle size of the pillared clay leads toobstruction of the filter paper and slow separation, requiring muchlonger filtration time and sequential filtrations because of the need toreplace the obstructed filter, for a preparative scale isolation of thepillared clay.

TABLE 2 Filtration rate comparison between a pillared clay slurry and aheterocoagulated clay slurry, each prepared with a 2.0 wt. % aqueousdispersion of HPM-20 clay Filtrate Total solids filtrate (initial at 20clay + Filtrate Filtrate minutes, ACH at 10 at 20 after 96 hr solidSupport type minutes minutes standing weight) Example (mmol Al/g clay)(g) (g) (g) (g) 45 Pillared clay — 39 206 1.4 (8.1)  (5.7 mmol Al/gclay) 44 Hetereocoagulate clay 224 — — 0.2 (5.8) (1.52 mmol Al/g clay)

Therefore in an aspect, this disclosure provides other methods ofquantifying filterability of the heteroadduct slurry demonstrates thatthe slurry can be considered readily filterable and readily filtered. Inone aspect, a composition such as the clay heteroadduct is readily oreasily filterable if the slurry is characterized by the followingfiltration behavior:

-   -   [a] when a 2.0 wt. % aqueous heteroadduct slurry is filtered        within a time period of 0 hours to 2 hours after the contacting        step b) (that is, after initial formation of the heteroadduct        slurry), the proportion of a filtrate obtained at a filtration        time of 10 minutes using either vacuum filtration or gravity        filtration, based upon the weight of the liquid carrier in the        slurry of the smectite heteroadduct is in a range of (1) from        about 50% to about 100% by weight of the liquid carrier in the        slurry before filtration, that is, of the initial slurry water        weight (2) from about 60% to about 100% by weight of the liquid        carrier in the slurry, (3) from about 70% to about 100% by        weight of the liquid carrier in the slurry, or (4) from about        80% to about 100% by weight of the liquid carrier in the slurry        before filtration; and    -   [b] the filtrate from the heteroadduct slurry, when evaporated,        yields solids comprising less than 20%, less than 15%, or less        than 10% of the initial combined weight of clay and        heterocoagulation agent.        The feature of performing the filtration with 0 to 2 hours after        the initial formation is specified because some non-heteroadduct        slurries including some pillared clay slurry compositions can be        filtered more easily after the slurry is allowed an initial        settling period of several days.

In the Examples used to produce the Table 2 data, the heteroadductslurry and the pillared clay slurry were filtered using a 20 micronfilter within several minutes after the contacting step between thecolloidal clay and the polymetallate. Essentially all of the water fromthe heteroadduct slurry had been filtered off at the 10 minute markafter initiating the vacuum filtration, while essentially none of thewater from the pillared clay slurry had been filtered off at 10 minutesafter initiating vacuum filtration. By assessing “readily filterable”using the combination of the two features recited above, it is notnecessary to specify either the filter spacings (for example, 20 μm) orwhether the filtration was conducted by a gravity filtration or vacuumfiltration. That is, a filter having a specified opening size can beeasily identified by the person of ordinary skill, for example the 20 μmfilter used in the examples, which allows the clay heteroadduct to meetboth of these criteria, but no filter size will allow the pillared clayto meet both of these criteria.

As an example of applying this “readily filterable” test, if a filterhaving too large of openings between the filter media is used, such thatthe pillared clay filtration meets the requirement of part [a] of thecriteria above, it will fail part [b] and will not be considered readilyfilterable. The clay heteroadduct will also fail part [b] when usingsuch a large filter size, but reducing the filter size (for example, toabout 20 μm) will allow the clay heteroadduct to meet both criteria [a]and [b], whereas the pillared clay will fail part [a] when reducing thefilter size, because the filter will clog and little or no liquidcarrier will be filtered through.

Similarly, either gravity or vacuum filtration can be used in the“readily filterable” test because at the point in time at which themeasurements of the filtrates is specified (10 minutes after initiatingthe filtration), a proper filter size can be easily identified by theperson of ordinary skill which will allow the clay heteroadduct to meetboth criteria [a] and [b], whereas the pillared clay will fail at leastone of criteria [a] and [b].

In another aspect, another method of quantifying filterability is asfollows. A composition such as the clay heteroadduct can be consideredreadily filterable or readily filtered if the slurry is characterized bythe following filtration behavior:

-   -   [a] when a 2.0 wt. % aqueous heteroadduct slurry is filtered        within a time period of 0 hours to 2 hours after the contacting        step b) to provide a first filtrate, the weight ratio of a        second filtrate to the first filtrate is less than 0.25, less        than 0.20, less than 0.10, less than 0.15, less than 0.10, less        than 0.5, or about 0.0, wherein the second filtrate is obtained        from filtration of a 2.0 wt. % slurry of a pillared clay        prepared using the colloidal smectite clay, the        heterocoagulation reagent, and the liquid carrier, and wherein        the weight of the first filtrate and the weight of the second        filtrate are measured after identical filtration times of 5        minutes, 10 minutes or 15 minutes; and    -   [b] the filtrate from the heteroadduct slurry, when evaporated,        yields solids comprising less than 20%, less than 15%, or less        than 10% of the initial combined weight of clay and        heterocoagulation agent.        Therefore, this test compares the filtrates collected from        slurries of the heteroadduct versus the pillared clay, whereas        the prior test compares the filtrate collected from a slurry of        the heteroadduct versus the aqueous carrier in the initial        slurry.

G. Metallocene Compounds

The calcined clay heteroadduct can be used as a substrate or catalystsupport-activator for one or more suitable polymerization catalystprecursors such as metallocenes, other organometallic compounds, and/ororganoaluminum compounds and the like, or other catalyst components inorder to prepare an olefin polymerization catalyst composition.Therefore, in one aspect, when a clay heteroadduct is prepared asdisclosed herein and combined with an organo-main group metal, such asalkylaluminum compounds and group 4 organotransition metal compound suchas a metallocene, an active olefin polymerization catalyst or catalystsystem is provided.

The support-activator of this disclosure can be used with metallocenecompounds (also referred to herein as metallocene catalysts) andco-catalysts such as organoaluminum compounds, the resulting compositionexhibits catalytic polymerization activity in the absence or substantialabsence of an ion-exchanged, protic-acid-treated, or pillared clay, oraluminoxane or borate activators. Previously, activators such asaluminoxane or borate activators have been thought of as necessary inorder to achieve polymerization catalytic activity with metallocene orsingle site or coordination catalyst systems. However, the combinationof heteroadduct support-activator, metallocene, and co-catalyst such asaluminum alkyl compound if desired to impart an activatable alkyl ligandto the metallocene provides an active catalyst with the need for otheractivators such as aluminoxane or borate activators.

Metallocene compounds are well-understood in the art, and the skilledperson will recognize that any metallocene can be used with thesupport-activator described in this disclosure, including for example,both non-bridged (non-ansa) metallocene compounds or bridged (ansa)metallocene compounds, or combinations thereof. Therefore, one, two, ormore metallocene compounds can be used with the clay heteroadductsupport-activators of this disclosure.

In one aspect, the metallocene can be a metallocene comprising a group 3to group 6 transition metal or a metallocene comprising a lanthanidemetal or a combination of more than one metallocene. For example, themetallocene can comprise a group 4 transition metal (titanium,zirconium, or hafnium). In a further aspect, the metallocene compoundcan comprises, consists of, consists essentially of, or is selected froma compound or a combination of compounds, each independently having theformula:

(X¹)(X²)(X³)(X⁴)M, wherein

-   -   a) M is selected from titanium, zirconium, or hafnium;    -   b) X¹ is selected from a substituted or an unsubstituted        cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl,        boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl,        wherein any substituent is selected independently from a halide,        a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, a C₁-C₂₀        organoheteryl, a fused C₄-C₁₂ carbocyclic moiety, or a fused        C₄-C₁₁ heterocyclic moiety having at least one heteroatom        selected independently from nitrogen, oxygen, sulfur, or        phosphorus;    -   c) X² is selected from: [1] a substituted or an unsubstituted        cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl,        wherein any substituent is selected independently from a halide,        a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀        organoheteryl; or [2] a halide, a hydride, a C₁-C₂₀ hydrocarbyl,        a C₁-C₂₀ heterohydrocarbyl, a C₁-C₂₀ organoheteryl, a fused        C₄-C₁₂ carbocyclic moiety, or a fused C₄-C₁₁ heterocyclic moiety        having at least one heteroatom selected independently from        nitrogen, oxygen, sulfur, or phosphorus;    -   d) wherein X¹ and X² are optionally bridged by at least one        linker substituent having from 2 to 4 bridging atoms selected        independently from C, Si, N, P, or B, wherein each available        non-bridging valence of each bridging atom is unsubstituted        (bonded to H) or substituted, wherein any substituent is        selected independently from, a halide, a C₁-C₂₀ hydrocarbyl, a        C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀ organoheteryl, and wherein        any hydrocarbyl, heterohydrocarbyl, or organoheteryl substituent        can form a saturated or unsaturated cyclic structure with a        bridging atom or with X¹ or X²;    -   e) [1] X³ and X⁴ are selected independently from a halide, a        hydride, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a        C₁-C₂₀ organoheteryl; [2] [GX^(A) _(k)X^(B) _(4-k)]⁻, wherein G        is B or Al, k is a number from 1 to 4, and X^(A) in each        occurrence is selected independently from H or a halide, and        X^(B) in each occurrence is selected independently from a C₁-C₁₂        hydrocarbyl, a C₁-C₁₂ heterohydrocarbyl, a C₁-C₁₂ organoheteryl;        [3] X³ and X⁴ together are a C₄-C₂₀ polyene; or [4] X³ and X⁴        together with M form a substituted or an unsubstituted,        saturated or unsaturated C₃-C6 metallacycle moiety, wherein any        substituent on the metallacycle moiety is selected independently        from a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl,        or a C₁-C₂₀ organoheteryl.

According to a further aspect, if desired, X¹ and X² can be bridged by alinker substituent selected from:

-   -   a) >EX⁵ ₂, -EX⁵ ₂EX⁵ ₂—, -EX⁵ ₂EX⁵EX⁵ ₂—, or >C═X⁵ ₂, wherein E        in each occurrence is independently selected from C or Si;    -   b) —BX⁵—, —NX⁵—, or —PX⁵—; or    -   c) [—SiX⁵ ₂(1,2-C₆H₄)SiX⁵ ₂—], [—CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂—], [—SiX⁵        ₂(1,2-C₆H₄)CX⁵ ₂—], [—SiX⁵ ₂(1,2-C₂H₂)SiX⁵ ₂—], [—CX⁵        ₂(1,2-C₆H₄)CX⁵ ₂—], or [—SiX⁵ ₂(1,2-C₆H₄)CX⁵ ₂—];    -   wherein X⁵ in each occurrence is selected independently from H,        a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a        C₁-C₂₀ organoheteryl;    -   and wherein any X⁵ substituents selected from hydrocarbyl,        heterohydrocarbyl, or organoheteryl substituent can form a        saturated or unsaturated cyclic structure with a bridging atom,        another X⁵ substituent, X¹, or X².        Examples of suitable linker substituents which can bridge X¹ and        X² include C₁-C₂₀ hydrocarbylene group, a C₁-C₂₀        hydrocarbylidene group, a C₁-C₂₀ heterohydrocarbyl group, a        C₁-C₂₀ heterohydrocarbylidene group, a C₁-C₂₀        heterohydrocarbylene group, or a C₁-C₂₀ heterohydrocarbylidene        group. For example, X¹ and X² can be bridged by at least one        substituent having the formula >EX⁵ ₂, -EX⁵ ₂EX⁵ ₂—, or —BX⁵—,        wherein E is independently C or Si, X⁵ in each occurrence is        selected independently from a halide, a C₁-C₂₀ aliphatic group,        a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphatic group, a        C₄-C₂₀ heteroaromatic group, or a C₁-C₂₀ organoheteryl group.

The Aspects section of this disclosure recites additional descriptionand selections regarding linking moieties between X¹ and X², regardingX⁵, and regarding specific linker substituents or X⁵ substituents.

The Aspects section of this disclosure also recites additionaldescription and selections for X¹ and X², including specificsubstituents on X¹ and X².

The Aspects section of this disclosure also recites additionaldescription and selections for X³ and X⁴, including specificsubstituents on X³ and X⁴.

The Aspects section of this disclosure also provides some specificexamples of metallocene compounds that are useful in combination withthe support-activator of this disclosure.

Metallocene compounds are understood by the person skilled in the art,who will recognize and appreciate the methods of making and using themetallocene in olefin polymerization catalyst systems. Many metallocenesand processes to make metallocenes and organotransition metal compoundsare known in the art, such as disclosed in U.S. Pat. Nos. 4,939,217;5,210,352; 5,436,305; 5,401,817; 5,631,335, 5,571,880; 5,191,132;5,480,848; 5,399,636; 5,565,592; 5,347,026; 5,594,078; 5,498,581;5,496,781; 5,563,284; 5,554,795; 5,420,320; 5,451,649; 5,541,272;5,705,478; 5,631,203; 5,654,454; 5,705,579; 5,668,230; 9,045,504; and9,163,100, and U.S. Patent Application Publication No. 2017/0342175, theentire disclosures of which are incorporated herein by reference.

H. Co-Catalysts

According to one aspect, this disclosure provides a catalyst compositionfor olefin polymerization, the catalyst composition comprising: a) atleast one metallocene compound; b) optionally, at least one co-catalyst;and c) at least one support-activator as described herein. Theco-catalyst includes compounds such as a trialkyl aluminum which arethought to impart a ligand to the metallocene which can initiatepolymerization when the metallocene is otherwise activated with thesupport-activator. The co-catalyst may be considered optional, forexample, in scenarios in which the metallocene may already include apolymerization-activatable/initiating ligand such as methyl or hydride.It will be understood that even when the metallocene compound includessuch as a polymerization-activatable/initiating ligand, a co-catalystcan be used for other purposes, such as to scavenge moisture from thepolymerization reactor or process. Thus, the co-catalyst can comprise orbe selected from, for example, an alkylating agent, a hydriding agent,or a silylating agent. The metallocene compound, the support-activator,and the co-catalyst can be contacted in any order.

The co-catalyst can comprises or can be selected from an organoaluminumcompound, an organoboron compound, an organozinc compound, anorganomagnesium compound, an organolithium compound, or any combinationthereof.

The Aspects section of this disclosure recites additional descriptionand selections for each of the organoaluminum compound, organoboroncompound, organozinc compound, organomagnesium compound, andorganolithium compound.

In an aspect, for example, the co-catalyst can comprise, consists of,consist essentially of, or be selected from at least one organoaluminumcompound which can independently have the formulaAl(X^(A))^(n)(X^(B))^(m), M^(x)[AlX^(A) ₄], Al(X^(C))_(n)(X^(D))_(3-n),M^(x)[AlX^(C) ₄], that is, can be neutral molecular compounds or ioniccompounds/salts of aluminum, wherein each of the variables of theseformulas is defined in the Aspects section of this disclosure. Forexample, the co-catalyst can comprise, consists of, consist essentiallyof, or be selected from trimethylaluminum, triethylaluminum (TEA),tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum,ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide,diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminumchloride, ethyl-(3-alkylcyclopentadiyl)aluminum, and the like, includingany combination thereof.

In another aspect, for example, the co-catalyst can comprise, consistsof, consist essentially of, or be selected from at least one organoboroncompound which can independently have the formulaB(X^(E))_(q)(X^(F))_(3-q) or M^(y)[BX^(E) ₄], that is, can be neutralmolecular compounds or ionic compounds/salts of boron, wherein each ofthe variables of these formulas is defined in the Aspects section ofthis disclosure. For example, the co-catalyst can comprise, consists of,consist essentially of, or be selected from trimethylboron,triethylboron, tripropylboron, tributylboron, trihexylboron,trioctylboron, diethylboron ethoxide, diisobutylboron hydride,triisobutylboron, diethylboron chloride, di-3-pinanylborane,pinacolborane, catecholborane, lithium borohydride, lithiumtriethylborohydride, and the like, including a Lewis base adductthereof, or any combination or mixture thereof. In another aspect, theco-catalyst can comprise or can be a halogenated organoboron compound,for example a fluorinated organoboron compound, examples of whichinclude tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination ormixture thereof.

In yet another aspect, for example, the co-catalyst can comprise,consists of, consist essentially of, or be selected from at least oneorganozinc or organomagnesium compound which can independently have theformula M^(C)(X^(G))_(r)(X^(H))_(2-r), wherein each of the variables ofthis formula is defined in the Aspects section of this disclosure. Forexample, the co-catalyst can comprise, consists of, consist essentiallyof, or be selected from dimethylzinc, diethylzinc, diisopropylzinc,dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium,n-butyl-sec-butylmagnesium, dicyclopentadienylmagnesium, ethylmagnesiumchloride, butylmagnesium chloride, and the like, including anycombination thereof.

In yet another aspect, for example, the co-catalyst can comprise,consists of, consist essentially of, or be selected from at least oneorganolithium compound which can independently have the formulaLi(X^(J)), wherein each of the variables of the formula(s) are definedin the Aspects section of this disclosure. For example, the co-catalystcan comprise, consists of, consist essentially of, or be selected frommethyllithium, ethyllithium, propyllithium, butyllithium (includingn-butyllithium and t-butyllithium), hexyllithium, iso-butyllithium, andthe like, or any combination thereof.

I. Optional Co-Activators

In an aspect, other activators in addition to the calcined smectiteheteroadduct activator support can be used in the catalyst compositionsof this disclosure if desired. These are referred to as co-activators,and examples of optional co-activators include but are not limited to anion-exchanged clay, a protic-acid-treated clay, a pillared clay, analuminoxane, a borate activator, an aluminate activator, an ionizingionic compound, a solid oxide treated with an electron withdrawinganion, or any combination thereof.

The Aspects section of this disclosure recites additional descriptionand selections for each of these optional co-activators.

Aluminoxanes. Aluminoxanes (also referred to as poly(hydrocarbylaluminum oxides) or organoaluminoxanes) can be used to contact the othercatalyst components, for example, in any solvent which is substantiallyinert to the reactants, intermediates, and products of the activationstep such as a saturated hydrocarbon solvent or a solvent such astoluene. The catalyst composition formed in this manner may be isolatedif desired or the catalyst composition may be introduced into thepolymerization reactor without being isolated.

As understood by the skilled artisan, aluminoxanes are oligomeric,wherein the aluminoxane compound can comprise linear structures, cyclic,or cage structures, or mixtures thereof. For example, cyclic aluminoxanecompounds having the formula (R—Al—O)_(n), wherein R can be a linear orbranched alkyl having from 1 to about 12 carbon atoms, and n can be aninteger from 3 to about 12. The (AlRO)_(n) moiety also constitutes therepeating unit in a linear aluminoxane, for example, having the formula:R(R—Al—O)_(n)AlR₂, wherein R can be a linear or branched alkyl havingfrom 1 to about 12 carbon atoms, and n can be an integer from 1 to about75. For example, the R group can be a linear or branched C₁-C₈ alkylsuch as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl,and wherein n can represent an integer from 1 to about 50. Dependingupon how the organoaluminoxane is prepared, stored, and used, the valueof n may be variable within a single sample of aluminoxane, and such acombination or population of organoaluminoxane species is usuallypresent in any sample.

Organoaluminoxanes can be prepared by various procedures known in theart, for example, organoaluminoxane preparations are disclosed in U.S.Pat. Nos. 3,242,099 and 4,808,561, each of which is incorporated byreference herein, in its entirety. In one aspect, an aluminoxane may beprepared by reacting water which is present in an inert organic solventwith an aluminum alkyl compound such as AlR₃ to form the desiredorganoaluminoxane compound. Alternatively, organoaluminoxanes may beprepared by reacting an aluminum alkyl compound such as AlR₃ with ahydrated salt, such as hydrated copper sulfate, in an inert organicsolvent.

In one embodiment, the aluminoxane compound can be methylaluminoxane,ethylaluminoxane, n-propylaluminoxane, iso-propyl-aluminoxane,n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane,3-pentyl-aluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, orcombinations thereof. In an aspect, methyl aluminoxane (MAO), ethylaluminoxane (EAO), or isobutyl aluminoxane (IBAO) can be used asoptional co-catalysts, and these aluminoxanes can be prepared fromtrimethylaluminum, triethylaluminum, or triisobutylaluminum,respectively. These compounds can be complex compositions, and aresometimes referred to as poly(methyl aluminum oxide), poly(ethylaluminum oxide), and poly(isobutyl aluminum oxide), respectively. Inanother aspect, aluminoxanes can be used in combination with atrialkylaluminium, such as disclosed in U.S. Pat. No. 4,794,096, whichis herein incorporated by reference in its entirety.

In preparing a catalyst composition comprising optional aluminoxane, themolar ratio of the aluminum present in the aluminoxane to themetallocene compound(s) in the composition can be lower than the typicalmolar ratio that would be used in the absence of the support-activatorof the present disclosure. In the absence of support-activators of thisdisclosure, aluminoxane amounts can be, for example, from about 1:10moles Al/moles metallocene (mol Al/mol metallocene) to about 100,000:1mol Al/mol metallocene or from about 5:1 mol Al/mol metallocene to about15,000:1 mol Al/mol metallocene. When used in combination with thedisclosed support-activators, the relative amounts of aluminoxane can bereduced. For example, the amount of optional aluminoxane added to apolymerization zone can be less than the previous typical amount withina range of about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L toabout 100 mg/L, or from about 1 mg/L to about 50 mg/L. Alternatively,aluminoxane can be used in an amount typically used in the prior art,but with the additional use of a support-activator of the presentdisclosure in order to obtain further advantages for such a combination.

Organoboron compounds. The catalyst compositions of this disclosure canalso comprise an optional organoboron co-activator if desired, inaddition to the recited components (support-activator, metallocene, andoptional co-catalyst). In one aspect, the organoboron compound cancomprise or be selected form neutral boron compounds, borate salts, orcombinations thereof. For example, the organoboron compounds cancomprise or be selected from a fluoroorgano boron compound, afluoroorgano borate compound, or a combination thereof, and any suchfluorinated compounds known in the art can be utilized.

Thus, the term fluoroorgano boron compound is used herein to refer tothe neutral compounds of the form BY₃, and the term fluoroorgano boratecompound is used herein to refer to the monoanionic salts of afluoroorgano boron compound of the form [cation]⁺[BY₄]⁻, where Yrepresents a fluorinated organic group. For convenience, fluoroorganoboron and fluoroorgano borate compounds are typically referred tocollectively by organoboron compounds, or by either name as the contextrequires.

In an aspect, examples of fluoroorgano boron compounds that can be usedas co-activators include, but are not limited to,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, including mixtures thereof. Examples of fluoroorganoborate compounds that can be used as optional co-activators include, butare not limited to, fluorinated aryl borates such as,N,N-dimethylanilinium tetrakis-(pentafluorophenyl)borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and the like, includingmixtures thereof.

The Aspects section of this disclosure recites additional descriptionand selections for the optional fluoroorgano boron and fluoroorganoborate compound co-activators.

Although not intending to be bound by theory, these fluoroorgano borateand fluoroorgano boron compounds are thought to form weakly-coordinatinganions when combined with metallocene compounds, as disclosed in U.S.Pat. No. 5,919,983, which is incorporated herein by reference in itsentirety.

Generally, any amount of organoboron compound can be utilized as anoptional co-activator. For example, in one aspect, the molar ratio ofthe organoboron compound to the metallocene compound in the compositioncan be from about 0.1:1 mole of organoboron or organoborate compound permole of metallocene (mol/mol) to about 10:1 mol/mol, or from about 0.5mol/mol to about 10 mol/mol (mole of organoboron or organoboratecompound per mole of metallocene), or alternatively in a range of fromabout 0.8 mol/mol to about 5 mol/mol (mole of organoboron ororganoborate compound per mole of metallocene). However, it will beappreciated that the amount can be reduced or adjusted downward in thepresence of a clay-heteroadduct support-activator.

Ionizing compounds. In a further aspect, the optional co-activatorswhich can be used in addition to the recited components of the catalystcompositions of this disclosure can comprise or can be selected fromionizing compounds. Examples of ionizing compound are disclosed in U.S.Pat. Nos. 5,576,259 and 5,807,938, each of which is incorporated hereinby reference, in its entirety.

The Aspects section of this disclosure recites additional descriptionand selections for the optional ionizing compound co-activators.

The term ionizing compound is term of art and refers to a compound,particularly an ionic compound, which can function to enhance activityof the catalyst composition. In one aspect, the fluoroorgano boratecompounds described herein as optional organoboron co-activators canalso be considered and function as ionizing compound co-activators.However, the scope of the ionizing compounds is broader than thefluoroorgano borate compounds, as compounds such as fluoroorganoaluminate are encompassed by ionizing compounds.

While not intending to be bound by theory, it is believed that theionizing compounds may be capable of interacting or reacting with themetallocene compound and converting the metallocene into a cationic oran incipient cationic metallocene compound, which activates themetallocene to polymerization activity. Again, while not intending to bebound by theory, it is believed that the ionizing compound may functionby completely or partially extracting an anionic ligand from themetallocene, particularly a non-cycloalkadienyl ligand or non-alkadienylligand such as (X³) or (X⁴) of the metallocene formula (X¹)(X²)(X³)(X⁴)Mdisclosed herein, to form a cationic or incipient cationic metallocene.However, the ionizing compound can function as an activator(co-activator) regardless of any mechanism by which it functions. Forexample, the ionizing compound may ionize the metallocene, abstract anX³ or X⁴ ligand in a fashion as to form an ion pair, weakens themetal-X³ or metal-X⁴ bond, or simply coordinate to an X³ or X⁴ ligand,or any other mechanisms by which activation may occur. Further, it isnot necessary that the ionizing compound activate (co-activate) themetallocene only, as the activation function of the ionizing compound isevident in the enhanced activity of catalyst composition as a whole, ascompared to a catalyst composition containing catalyst composition thatdoes not comprise any ionizing compound.

Examples of ionizing compounds include, but are not limited to, the listof compounds presented in the Aspects section of this disclosure.

Optional Support-Activators. In a further aspect, the optionalco-activators which can be used in addition to the recited components ofthe catalyst compositions of this disclosure can comprise or can beselected from other support-activators, sometimes termedactivator-supports, which when used in the catalyst compositionsdescribed herein are termed co-activator-supports. Examples of optionalco-activator-supports are disclosed in U.S. Pat. Nos. 6,107,230;6,653,416; 6,992,032; 6,984,603; 6,833,338; and 9,670,296 each of whichis incorporated herein by reference, in its entirety.

For example, the optional co-activator-support may comprise or beselected from silica, alumina, silica-alumina, or silica-coated aluminawhich is treated with at least one electron-withdrawing anion. Forexample, the silica-coated alumina can have a weight ratio ofalumina-to-silica in a range of from about 1:1 to about 100:1, or fromabout 2:1 to about 20:1, in this aspect. The at least oneelectron-withdrawing anion can comprise or be selected from fluoride,chloride, bromide, phosphate, triflate, bisulfate, sulfate, and thelike, or combinations thereof.

In an aspect, the optional co-activator-supports can be selected from,for example, fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, and the like, any ofwhich or any combinations of which can be employed in catalystcompositions disclosed herein. Alternatively, or additionally, theco-activator-support can comprise or be selected from solid oxidestreated with an electron withdrawing anion such as fluoridedsilica-alumina, or sulfated alumina and the like.

Examples of co-activator-supports can include, but are not limited to,those listed in the Aspects section of this disclosure.

J. Preparation of Catalyst Compositions

In the catalyst system the relative concentration or ratio ofmetallocene such as a group 4 metallocene of the formula(X¹)(X²)(X³)(X⁴)M to the calcined clay heteroadduct can be expressed asmoles of M (metal) per grams of calcined clay heteroadduct (mol M/gheteroadduct). In one aspect, it has been found that the ratio of molesof M per grams of calcined clay heteroadduct can be in a range of fromabout 0.025 mol M/g heteroadduct to about 0.000000005 mol M/gheteroadduct. In another aspect, the moles of M per grams of calcinedclay heteroadduct can be used in a range of from about 0.0005 mol M/gheteroadduct to about 0.00000005 mol M/g heteroadduct, or alternatively,from about 0.0001 mol M/g heteroadduct to 0.000001 mol M/g heteroadduct.As in all ranges disclosed herein, these recited ranges include the endpoints as well as intermediate values and subranges within the recitedrange. These ratios reflect the catalyst recipe, that is, these ratiosare based on the amount of the components combined to give the catalystcomposition, regardless of what the ratio may be in the final catalyst.

In the catalyst system the relative concentration or ratio ofco-catalyst to the calcined clay heteroadduct can be expressed as molesof co-catalyst (for example, organoaluminum compound) per grams ofcalcined clay heteroadduct (mol co-catalyst/g heteroadduct). In oneaspect, it has been found that the ratio of moles of co-catalyst such asan organoaluminum compound per grams of calcined clay heteroadduct canbe in a range of from about 0.5 mol co-catalyst/g heteroadduct to about0.000005 mol co-catalyst/g heteroadduct. In another aspect, the ratio ofmoles of co-catalyst per grams of calcined clay heteroadduct that can beused is in a range of from about 0.1 mol co-catalyst/g heteroadduct toabout 0.00001 mol co-catalyst/g heteroadduct, or alternatively, fromabout 0.01 mol co-catalyst/g heteroadduct to about 0.0001 molco-catalyst/g heteroadduct.

Catalyst compositions can be produced by contacting the transition metalcompound such as a metallocene, the calcined clay heteroadduct, and theco-catalyst such as an organoaluminum compound under suitableconditions. Contacting can occur in any number of ways, for example byblending, by contact in a carrier liquid, by feeding each component intoa reactor separately or in any order or combination. For example,various combinations of the components or compounds can be contactedwith one another before being further contacted in a reactor with theremaining compound(s) or component(s). Alternatively, all threecomponents or compounds can be contacted together before beingintroduced into a reactor. Regarding the additional optional componentswhich can be used in the catalyst system disclosed herein, such asco-activators, ionizing ionic compounds, and the like, contacting stepsusing these optional components can occur in any way and in any order.

In one aspect, the catalyst composition can be prepared by firstcontacting a transition metal compound such as a metallocene, with aco-catalyst such as an organoaluminum compound, for a time period offrom about 1 minute to about 24 hours, or alternatively from about 1minute to about 1 hour, at a contact temperature that can range fromabout 10° C. to about 200° C., alternatively from about 12° C. to about100° C., alternatively from about 15° C. to about 80° C., oralternatively from about 20° C. to about 80° C., to form a firstmixture, and this first mixture can then be contacted with a calcinedclay heteroadduct to form the catalyst composition.

In another aspect, the metallocene, the co-catalyst such as anorganoaluminum compound, and the calcined clay heteroadduct can bepre-contacted before being introduced into a reactor. For example, thepre-contacting step may occur over a time period of from about 1 minuteto about 6 months. In one aspect, for example, the pre-contacting stepmay occur over a time period of from about 1 minute to about 1 week at atemperature from about 10° C. to about 200° C. or from about 20° C. toabout 80° C., to provide the active catalyst composition. Further, anysubset of the final catalyst components also can be pre-contacted in oneor more pre-contacting steps, each with its own pre-contacting timeperiod.

After pre-contacting any or all of the catalyst system components, thecatalyst composition can be said to comprise post-contacted components.For example, a catalyst composition can comprise a post-contactedmetallocene, a post-contacted co-catalyst such as an organoaluminumcompound, and a post-contacted calcined clay heterodduct component. Itis not uncommon in the field of catalyst technology that the specificand detailed nature of the active catalytic site and the specific natureand fate of each component used to make the active catalyst are notprecisely known. While not intending to be bound by theory, the majorityof the weight of the catalyst composition based upon the relativeweights of the individual components can be thought of as comprising thepost-contacted calcined clay heteroadduct. Because the nature of theactive site and post-contacted components are not precisely known, thecatalyst composition may simply be described according to its componentsor referred to as comprising post-contacted compounds or components.

The polymerization activity of the catalyst composition can be expressedas the weight of polymer polymerized per weight of support-activatorcomprising the calcined smectite heteroadduct, per unit of time, forexample, gram polymer/gram (calcined) support-activator/hour (g/g/hr).That is, activity can be calculated on the basis of thesupport-activator alone, absent any metallocene or co-catalystcomponents. This measurement allows comparisons of the various activatorsupports, including with other activators, where the metallocene,co-catalyst, and other conditions are the same or substantially thesame. The activity values disclosed in the Examples were measured underslurry polymerization conditions, using isobutane as the diluent, unlessotherwise specified, and with a polymerization temperature of from about50° C. to about 150° C., (for example at a temperature of 90° C.), andusing a combined ethylene and isobutane pressure in a range of fromabout 300 psi to about 800 psi, for example 450 psi for the totalcombined ethylene and isobutane. Activity data are reported as theweight of polymer produced divided by the weight of calcined clayheteroadduct per hour.

Catalyst activity can be a function of the metallocene and the calcinedclay heteroadduct, as well as other components and conditions. Under theconditions explained above, the activity based on the weight of thecalcined clay heteroadduct can be greater than about 1,000 grams ofpolyethylene polymer per gram of calcined clay heteroadduct per hour (gPE/g heteroadduct/hr, or simply, g/g/hr). In another aspect, theactivity based on the weight of the calcined clay heteroadduct can begreater than about 2000 g/g/hr, greater than about 4,000 g/g/hr, greaterthan about 6,000 g/g/hr, greater than about 8,000 g/g/hr, greater thanabout 10,000 g/g/hr, greater than about 15,000 g/g/hr, greater thanabout 25,000 g/g/hr, or greater than about 50,000 g/g/hr. The upperlimit for each of these activities can be about 70,000 g/g/hr, such thatthe activities can range from greater than these disclosed values, andless than about 75,000 g/g/hr.

For example, in an aspect and using the conditions described herein, theactivator supports can have a polymerization activity of about 500g/g/hr, about 750 g/g/hr, about 1,000 g/g/hr, about 1,250 g/g/hr, about1,500 g/g/hr, 1,750 g/g/hr, about 2,000 g/g/hr, about 2,500 g/g/hr,about 3,500 g/g/hr, about 5,000 g/g/hr, about 7,500 g/g/hr, about 10,000g/g/hr, about 12,500 g/g/hr, about 15,000 g/g/hr, about 17,500 g/g/hr,about 20,000 g/g/hr, about 25,000 g/g/hr, about 30,000 g/g/hr, about35,000 g/g/hr, about 40,000 g/g/hr, about 50,000 g/g/hr, about 60,000g/g/hr, about 70,000 g/g/hr, or about 75,000 g/g/hr, including anyranges between these values. The higher values of polymerizationactivity can be associated with clay supports having extremely sitedensities, and these activity values also can be metallocene dependent.Therefore, by applying the teachings herein, activity levels can beachieved that are in a range between two of the recited values recited,for example, activity levels can be obtained in the range of 500-75,000g/g/hr, in the range as well as intermediate values and ranges such as1,000-50,000 g/g/hr, 2,000-40,000 g/g/hr, or 2,500-20,000 g/g/hr. Theactivities of the Examples and in the data tables were measured underslurry homopolymerization conditions, using isobutane as the diluent,and with a polymerization temperature of 90° C., and a combined ethyleneand isobutane pressure of 450 total psi and(1-n-butyl-3-methyl-cyclopentadienyl)₂ZrCl₂ and triethylaluminumcatalyst composition unless otherwise noted.

In one aspect, no aluminoxane such as methyl aluminoxane was needed toactivate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound which can greatlyincrease the polymer production costs. Further, in another aspect, noorganoboron compound or ionizing compound, such as borate compounds,were required to in order to activate the metallocene and form thecatalyst composition. Further, ion-exchanged, protic-acid-treated orpillared clays, which require similarly multi-step preparations whichincrease costs, were also not required to activate the metallocene andform the catalyst composition. Therefore, an active heterogeneouscatalyst composition can be easily and inexpensively produced and usedfor polymerizing olefin monomers including comonomers if desired in theabsence of any aluminoxane compounds, boron compounds or boratecompounds, ion-exchanged-, protic-acid-treated- or pillared-clays.Although MAO or other aluminoxanes, boron or borate compounds,ion-exchanged-clays, protic-acid-treated-clays, or pillared-clays arenot required in the disclosed catalyst systems, these compounds can beused in reduced amounts or typical amounts according to other aspects ofthe disclosure.

K. Polyolefins and Polymerization Processes

In an aspect, this disclosure describes a process of contacting at leastone olefin monomer and the disclosed catalyst composition to produce atleast one polymer (polyolefin). The term “polymer” is used herein toinclude homopolymers, copolymers of two olefin monomers, and polymers ofmore than two olefin monomers such as terpolymers. For convenience,polymers of two or more than two olefin monomers are referred to assimply copolymers. Thus, the catalyst composition can be used topolymerize at least one monomer to produce a homopolymer or a copolymer.

In an aspect, homopolymers are comprised of monomer residues which havefrom 2 to about 20 carbon atoms per molecule, preferably 2 to about 10carbon atoms per molecule. The olefin monomer can comprise or beselected from ethylene, propylene, 1-butene, 3-methyl-1-butene,1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixturesthereof. In one aspect, homopolymers of ethylene, homopolymers ofpropylene, and homopolymers of other olefins are encompassed by thisdisclosure. In another aspect, copolymers of ethylene and at least onecomonomer and less commonly, copolymers of two non-ethylene copolymers,are encompassed by this disclosure.

When a copolymer is desired, each monomer may have from about 2 to about20 carbon atoms per molecule. Comonomers of ethylene can include, butare not limited to, aliphatic 1-olefins having from 3 to 20 carbon atomsper molecule, such as, for example, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene, styrene, vinylcyclohexane andother olefins, and conjugated or non-conjugated diolefins such as1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene,1,4-pentadiene, 1,7-hexadiene, and other such diolefins and mixturesthereof. In a further aspect, ethylene can be copolymerized with atleast one comonomer comprising or selected from 1-butene,4-methyl-1-pentene, 1-hexene, 1-octene, or 1-decene. An amount ofcomonomer can be introduced into a reactor zone which is sufficient toproduce a copolymer that can incorporate from about 0.01 wt. % to about10 wt. % comonomer or even beyond this range, based upon the totalweight of the monomer and comonomer in the copolymer; alternatively,from about 0.01 wt. % to about 5 wt. % comonomer; alternatively still,from about 0. 1 wt. % to about 4 wt. % comonomer; or alternativelystill, any amount of comonomer can be introduced into a reactor zonethat provides a desired copolymer.

Typically, the catalyst composition can be used to homopolymerizeethylene, or propylene, or copolymerize ethylene with a comonomer, orcopolymerize ethylene and propylene. In another aspect, severalcomonomers may be polymerized with monomer in the same or differentreactor zones to achieve the desired polymer properties.

Other useful comonomers can include polar vinyl, conjugated andnon-conjugated dienes, acetylene and aldehyde monomers, which can beincluded for example in minor amounts in terpolymer compositions. Forexample, non-conjugated dienes useful as comonomers can be straightchain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes havingfrom 6 to 15 carbon atoms. Suitable non-conjugated dienes can include,for example: (a) straight chain acyclic dienes, such as 1,4-hexadieneand 1,6-octadiene; (b) branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and3,7-dimethyl-1,7-octadiene; (c) single ring alicyclic dienes, such as1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,7-cyclododecadiene; (d)multi-ring alicyclic fused and bridged ring dienes, such astetrahydroindene; norbornadiene; methyl-tetrahydroindene;dicyclopentadiene (DCPD); bicyclo-(2.2.1)-hepta-2,5-diene; alkenyl,alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); and (e)cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allylcyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene,and vinyl cyclododecene. Particularly useful non-conjugated dienesinclude dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene,5-ethylidene-2-norbornene, and tetracyclo-(.Δ-11,12)-5,8-dodecene.Particularly useful diolefins include 5-ethylidene-2-norbornene (ENB),1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and5-vinyl-2-norbornene (VNB). Note that throughout this description theterms “non-conjugated diene” and “diene” are used interchangeably.

The catalyst compositions can be used for polymerizing olefins to makeoligomeric and polymeric materials having a wide range of densities, forexample, in a range of from about 0.66 g/mL (also, g/cc) to about 0.96g/mL, which are used in numerous applications. The catalyst compositionsdisclosed herein are particularly useful for the production ofcopolymers. For example, copolymer resins may have a density of 0.960g/cc or less, preferably 0.952 g/cc or less, or more preferably 0.940g/cc or less. In accordance with certain aspects of the presentdisclosure, it is possible to achieve densities of less than 0.91 g/ccand even as low as 0.860 g/cc. When describing a density as less than aspecific density, one lower limit of such densities can be about 0.860g/cc. Copolymer resins can contain at least about 65 wt. % (percent byweight) of ethylene units, that is, the weight percent of ethylenemonomers actually incorporated into the copolymer resin. In anotheraspect, the copolymer resins of this disclosure can contain at leastabout 0.5 wt. %, for example, from 0.5 wt. % to 35 wt. % of analpha-olefin (α-olefin), referring to the weight percent of alpha-olefincomonomers actually incorporated into the copolymer resin.

The catalyst compositions prepared according to the present disclosureare also useful for preparing: (a) ethylene/propylene copolymers,including “random copolymer” in which the commoner is distributedrandomly along the polymer back-bone or chain; (b) “propylene randomcopolymer”, in which a random copolymer of propylene and ethylenecomprising about 60 wt. % of the polymer derived from propylene units;and (c) “impact copolymer” meaning two or more polymers in which onepolymer is dispersed in the other polymer, typically one polymercomprising a matrix phase and the other polymer comprising an elastomerphase. The catalyst compositions described herein may further be used toprepare polyalphaolefins with monomers containing more than threecarbons. Such oligomers and polymers are particularly useful, forexample, as lubricants.

Any number of polymerization methods or processes can be used with thecatalyst compositions of this disclosure. For example, slurrypolymerization, gas phase polymerization, and solution polymerizationand the like, including multi-reactor combinations thereof, can be used.Multi-reactor combinations can be configured in a serial or parallelconfiguration, or a combination thereof, depending upon the desiredpolymerization sequence. Examples of reactor systems and combinationscan include, for example, dual slurry loops in series, multiple slurrytanks in series, or slurry loop combined with gas phase, or multiplecombinations of these processes, in which polymerization of ethylene,propylene and alpha-olefins separately or together can be carried out.In another aspect, gas phase reactors can comprise fluidized bedreactors or tubular reactors, slurry reactors can comprise verticalloops or horizontal loops or stirred tanks, and solution reactors cancomprise stirred tank or autoclave reactors. Thus, any polymerizationzone known in the art which can produce polyolefins such as ethylene andalpha-olefin-containing polymers including polyethylene, polypropylene,ethylene alpha-olefin copolymers, as well as more generally tosubstituted olefins such as vinylcyclohexane, can be utilized. In anaspect, for example, a stirred reactor can be utilized for a batchprocess, and then the reaction can be carried out continuously in a loopreactor or in a continuous stirred reactor or in a gas phase reactor.

The catalyst compositions comprising the recited components canpolymerize olefins in the presence of a diluent or liquid carrier, andthese two terms are used interchangeably herein, even if a catalystcomponent is not soluble in the diluent or liquid carrier. Suitablediluents used in slurry and solution polymerization are known in the artand include hydrocarbons which are liquid under reaction conditions.Further, term “diluent” as used in this disclosure does not necessarilymean that the material is inert, as it is possible that a diluent cancontribute to polymerization such as in bulk polymerizations withpropylene.

Suitable hydrocarbon diluents can include, but are not limited tocyclohexane, isobutane, n-butane, propane, n-pentane, isopentane,neopentane, and n-hexane, and higher boiling solvents such as ISOPAR™and the like. Isobutane works well as the diluent in a slurrypolymerization. Examples of such slurry polymerization technologies canbe found in U.S. Pat. Nos. 4,424,341; 4,501,885; 4,613,484; 4,737,280;and 5,597,892; the entire disclosures of which are incorporated hereinby reference. When polymerizing propylene, or other alpha-olefins, thepropylene or alpha-olefin itself can comprise the solvent, which areknown in the art as bulk polymerizations.

In various aspects and embodiments, polymerization reactors suitable foruse with the catalyst system can comprise at least one raw material feedsystem, at least one feed system for catalyst or catalyst components, atleast one reactor system, at least one polymer recovery system or anysuitable combination thereof. Suitable reactors can further compriseany, or combination of, a catalyst storage system, an extrusion system,a cooling system, a diluent recycling system, a monomer recyclingsystem, and comonomer recycling system or a control system. Suchreactors can comprise continuous take-off and direct recycling of thecatalyst, diluent, monomer, comonomer, inert gases, and polymer asdesired. In one aspect, continuous processes can comprise the continuousintroduction of a monomer, a comonomer, a catalyst, a co-catalyst ifdesired, and a diluent into a polymerization reactor and the continuousremoval from this reactor of a suspension comprising polymer particlesand the diluent.

In one aspect, the polymerization methods can be carried out over a widetemperature range, for example, the polymerization temperatures may bein a range of from about 50° C. to about 280° C., and in another aspect,polymerization reaction temperatures may be in a range of from about 70°C. to about 110° C. The polymerization reaction pressure can be anypressure that does not terminate the polymerization reaction. In oneaspect, polymerization pressures may be from about atmospheric pressureto about 30000 psig. In another aspect, polymerization pressures may befrom about 50 psig to about 800 psig.

The polymerization reaction can be carried out in an inert atmosphere,that is, in an atmosphere substantially free of molecular oxygen andunder substantially anhydrous conditions;

thus, in the absence of water as the reaction begins. Therefore a dry,inert atmosphere, for example, dry nitrogen or dry argon, is typicallyemployed in the polymerization reactor.

In an aspect, hydrogen can be used in a polymerization process tocontrol polymer molecular weight. In another aspect a method ofdeactivating a catalyst, by adding carbon monoxide to the polymerizationzone as described in U.S. Pat. No. 9,447,204, which is incorporated byreference herein, may be used to mitigate or stop an uncontrolled, orrunaway polymerization.

For the catalyst systems of this disclosure, the polymerizationsdisclosed herein are commonly carried out using a slurry polymerizationprocess in a loop reaction zone or a batch process, or a gas phase zoneutilizing a fluidized bed or a stirrer bed.

Slurry loop. In one aspect, a typical polymerization method is a slurrypolymerization process (also known as the “particle form process”),which is disclosed, for example in U.S. Pat. No. 3,248,179, which isincorporated herein by reference. Other polymerization methods forslurry processes can employ a loop reactor of the type disclosed in U.S.Pat. No. 3,248,179, and those utilized in a plurality of stirredreactors either in series, parallel, or combinations thereof.

The polymerization reactor system can comprise at least one loop slurryreactor, and can include vertical or horizontal loops or a combination,which can independently be selected from a single loop or a series ofloops. Multiple loop reactors can comprise both vertical and horizontalloops. The slurry polymerization can be performed in an organic solventas the carrier or diluent. Examples of suitable solvents includepropane, hexane, cyclohexane, octane, isobutane, or combinationsthereof. Olefin monomer, carrier, catalyst system components, and anycomonomer can be continuously fed to a loop reactor where polymerizationoccurs. Reactor effluent can be flash evaporated to separate the solidpolymer particles.

Gas phase. In one aspect, a method for producing polyolefin polymersaccording to the disclosure is a gas phase polymerization process, usingfor example a fluidized bed reactor. This type reactor, and means foroperating the reactor, are described in, for example, U.S. Pat. Nos.3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400;5,352,749; 5,541,270; EP-A-0 802 202, Belgian Patent No. 839,380, eachof which is incorporated herein by reference. These patents disclose gasphase polymerization processes wherein the polymerization medium iseither mechanically agitated or fluidized by the continuous flow of thegaseous monomer and diluent.

Gas phase polymerization systems can employ a continuous recycle streamcontaining one or more monomers continuously cycled through thefluidized bed in the presence of the catalyst under polymerizationconditions. The recycle stream can be withdrawn from the fluidized bedand recycled back into the reactor. Simultaneously, polymer product canbe withdrawn from the reactor and fresh monomer can be added to replacethe polymerized monomer. Such gas phase reactors can comprise a processfor multi-step gas-phase polymerization of olefins, in which olefins arepolymerized in the gaseous phase in at least two independent gas-phasepolymerization zones while feeding a catalyst-containing polymer formedin a first polymerization zone to a second polymerization zone.

Other gas phase processes contemplated by the disclosed polymerizationprocess include series or multistage polymerization processes. In anaspect, gas phase processes that can be used in accordance with thedisclosure include those described in U.S. Pat. Nos. 5,627,242,5,665,818 and 5,677,375, and European publications EP-A-0 794 200,EP-B1-0 649 992, EP-A-0 802 202, and EP-B-634 421 all of which areincorporated herein by reference.

In an aspect of the gas phase polymerizations according to thisdisclosure, the ethylene partial pressure may vary in a range suitablefor providing practical polymerization conditions, for example, in arange of from 10 psi to 250 psi, for example, from 65 psi to 150 psi,from 75 psi to 140 psi, or from 90 psi to 120 psi. In another aspect, amolar ratio of comonomer to ethylene in the gas phase also may vary in arange suitable for providing practical polymerization conditions, forexample, in a range of from 0.0 to 0.70, from 0.0001 to 0.25, morepreferably from 0.005 to 0.025, or from 0.025 to 0.05. According to anaspect, the reactor pressure can be maintained in a range suitable forproviding practical polymerization conditions, for example, in a rangeof from 100 psi to 500 psi, from 200 psi to 500 psi, or from 250 psi to350 psi, and the like.

According to further aspects, in a fluidized gas bed process used forproducing polymers, a gaseous stream containing one or more monomers canbe continuously cycled through a fluidized bed in the presence of acatalyst under reactive conditions. The gaseous stream can be withdrawnfrom the fluidized bed and recycled back into the reactor, andsimultaneously, polymer product can be withdrawn from the fluidized bedand withdrawn from the reactor, while fresh monomer can be added toreplace the polymerized monomer. See, for example, U.S. Pat. Nos.4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922;5,436,304; 5,543,471; 5,462,999; 5,616,661; and 5,668,228; each of whichis incorporated herein by reference in its entirety.

In another aspect, antistatic compounds can be fed simultaneous with thefinished catalyst into a polymerization zone. Alternatively, antistaticcompounds such as those described in US Pat. Nos. 7,919,569; 6,271,325;6,281,306; 6,140,432 and 6,117,955, each of which is incorporated hereinby reference in its entirety, can be used. For example, the the clayheteroadduct can be contacted with or impregnated with one or moreantistatic compounds. Antistatic compounds may be added at any point,for example, they can be added any time after calcination such as up toand including the final post-contacted catalyst preparation.

In another aspect, so-called “self-limiting” compositions may be addedto the clay heteroadduct to inhibit chunking, fouling, or uncontrolledor runaway reaction in the polymerization zone. For example, U.S. Pat.Nos. 6,632,769; 6,346,584; and 6,713,573, each of which is incorporatedherein by reference, disclose additives that can release a catalystpoison above a threshold temperature. Typically, such compositions canbe added at any time after calcination, in order to limit or stoppolymerization activity above a desired temperature.

Solution. The polymerization reactor also can comprise a solutionpolymerization reactor, in which the monomer is contacted with thecatalyst composition by suitable stirring or other means. Solutionpolymerizations can be effected in a batch manner, or in a continuousmanner. A carrier comprising an inert organic diluent or excess monomercan be employed, and the polymerization zone is maintained attemperatures and pressures that will result in the formation of asolution of the polymer in the reaction medium. Agitation can beemployed during polymerization to obtain better temperature control andto maintain uniform polymerization mixtures throughout thepolymerization zone, and adequate means are utilized for dissipating theexothermic heat of polymerization. The reactor also can comprise aseries of at least one separator that employs high pressure and lowpressure to separate the desired polymer.

Tubular reactors and high pressure LDPE. In still another aspect, thepolymerization reactor can comprise a tubular reactor, which can makepolymers by free radical initiation or alternatively by employing thedisclosed catalysts. Tubular reactors can have several zones where freshmonomer, initiators, or catalysts and cocatalysts are added. Forexample, monomer can be entrained in an inert gaseous stream andintroduced at one zone of the reactor, and initiators, the catalystscomposition and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. These gas streamscan then be intermixed for polymerization, in which heat and pressurecan be appropriately adjusted to obtain optimal polymerization reactionconditions.

Combined or multiple reactors. In a further aspect, the catalysts andprocesses of this disclosure are not limited by possible reactor typesor combinations of reactor types. For example, the disclosed catalystsand processes can be used in multiple reactor systems which can comprisereactors combined or connected to perform polymerizations, or multiplereactors that are not connected. The polymer can be polymerized in onereactor under one set of conditions, and then the polymer can betransferred to a second reactor for polymerization under a different setof conditions.

In this aspect, the polymerization reactor system can comprise thecombination of two or more reactors. Production of polymers in multiplereactors can include several stages in at least two separatepolymerization reactors interconnected by a transfer device to transferthe polymers resulting from the first polymerization reactor into thesecond reactor, in which polymerization conditions are different in theindividual reactors. Alternatively, polymerization in multiple reactorscan include the manual transfer of polymer from one reactor tosubsequent reactors for continued polymerization. Such reactors caninclude any combination including, but not limited to, multiple loopreactors, multiple gas reactors, a combination of loop and gas reactors,a combination of autoclave reactors or solution reactors with gas orloop reactors, multiple solution reactors, or multiple autoclavereactors, and the like.

Polymers produced using the disclosed catalysts and processes. Thecatalyst compositions used in this process can produce high qualitypolymer particles without substantially fouling the reactor. When thecatalyst composition is used in a loop reactor zone under slurrypolymerization conditions, the particle size of the calcinedheterocoagulated product can be in a range of from about 10 microns (μm)to about 1000 microns, from about 25 microns to about 500 microns, fromabout 50 microns to about 200 microns, or from about 30 microns to about100 microns to provide good control of the polymer particle productionduring polymerization.

When the catalyst composition is used in a gas phase reactor zone, theparticle size of the calcined heterocoagulated product can be in a rangeof from about 1 micron to about 1000 microns, from about 5 to about 500microns, or from about 10 microns to about 200 microns, or from about 15microns to about 60 microns, to provide good control of the polymerparticle and polymerization reaction.

The suitable particle size in other polymerization reactor systems,whether single or multiple systems in series can be a function of thetotal productivity of the catalyst and the optimal particle size andparticle size distribution of the final polymer-catalyst compositeparticle. For example, the optimal size and size distribution can bedetermined by the polymerization reactor system, such as whether theparticles are easily fluidizable in a gas phase system but sufficientlylarge that they are not entrained in the fluidizing gas, which canresult in plugging downstream filters. Likewise, the optimal size andsize distribution in the polymerization system may be balanced againstthe ease with which they are conveyed or handled in storage silos orextrusion facilities when the catalyst-polymer composite particles aremelted and extruded into pellets.

Polymers produced using the catalyst composition of this disclosure canbe formed into various articles, such as, for example, householdcontainers and utensils, film products, car bumper components, drums,fuel tanks, pipes, geomembranes, and liners. In an aspect, additives andmodifiers can be added to the polymer in order to provide desiredeffects, such as a desired combination of physical, structural and flowproperties. It is believed that by using the methods and materialsdescribed herein, articles can be produced at a lower cost, whilemaintaining desired polymer properties obtained for polymers producedusing transition metal or metallocene catalyst compositions as disclosedherein.

Specific embodiments. In more specific embodiments of this disclosure,there is provided a process to produce a catalyst composition, theprocess comprising (optionally, “consisting essentially of”, or“consisting of”):

-   -   (1) contacting a suitable dioctahedral phyllosilicate clay, with        a heterocoagulation agent, to form a solid that is easily        filtered and washed to a conductivity of less than 10 mS/cm, or        less than 5 mS/cm, or between 1 mS/cm and 50 μS/cm, or between        500 μS/cm and 50 μS/cm;    -   (2) dehydrating and dehydroxylating the washed, clay        heteroadduct at a temperature or temperatures within a range of        from about −10° C. to about 500° C. to produce a calcined        heterocoagulated clay-adduct composition exhibiting no, or        substantially no d001 peak of 2 theta less than 8 degrees, and        preferably exhibiting no, or substantially no d001 peak of 2        theta less than 10 degrees. If there are peaks in the region        less than 10 degrees 2 theta, the major peak among them is not        less than 4 degrees 2 theta, or a peak greater in intensity than        that which would be exhibited by the clay mineral itself after        calcination at 300° C., such as from 8 degrees 2 theta to 12        degrees 2 theta;    -   (3) combining the calcined heterocoagulated clay-adduct        composition and a metallocene, for example,        bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride, at a        temperature in the range of from 15° C. to 100° C. to produce a        mixture; and    -   (4) after between 1 minute and 1 hour, combining the mixture in        part (3) and a trialkylaluminum, for example, triethylaluminum,        trioctylaluminum or triisobutylaluminum to produce the catalyst        composition.        An alternative specific embodiment to that set out immediately        above is to reverse the order of addition of the metallocene and        the trialkylaluminum in steps (1) through (4) immediately above.

EXAMPLES

The foregoing description is intended to illustrate and not limit thescope of the present disclosure, which is further illustrated by thefollowing examples. The examples are not to be construed as imposinglimitations upon the scope of the disclosure. Rather, it is to beunderstood that recourse can be had to various other embodiments,aspects, modifications, and equivalents thereof which, in view of thewritten description, may suggest themselves to the person of ordinaryskill in the art without departing from the spirit of the presentinvention or the scope of the appended claims. Therefore the followingexamples are put forth so as to provide those skilled in the art with amore detailed disclosure and description.

Reagents and General Procedures

Unless otherwise noted, all reagents used to prepare theclay-heteroadducts of this disclosure were obtained from the commercialsources indicated and used “as-is”.

Volclay® HPM-20 bentonite aqueous dispersion (montmorillonite)manufactured by American Colloid Company was obtained from McCullough &Associates, and is also referred to as simply HPM-20 or HPM-20 clay. A50% aluminum chlorhydrate aqueous solution (abbreviated “ACH”) andUltraPAC® 290 (polyaluminum chloride, empirically Al₂(OH)_(2.5)Cl_(3.5))were obtained from GEO Specialty Chemicals. Aluminum chlorhydrate powder(ALOXICOLL® 51P, empirically Al₂Cl(OH)₅) and aluminumsesquichlorohydrate solution (ALOXICOLL® 31L) were obtained from ParchemFine and Specialty Chemicals. Fumed Silica (AEROSIL® 200) and fumedaluminum oxide aqueous dispersion (AERODISP® W400) were obtained fromEvonik Industries AG. An aqueous dispersion of colloidal alumina(NYACOL® AL27) was obtained from Nano Technologies, Inc.

Unless noted otherwise, in the specification and examples, the claydispersions, clay heteroadducts, pillared clays, and other compositionscould be prepared using a dual-speed Conair™ Waring™ Commerical LabBlender model 7010G, equipped with timer. Blender speeds may be referredto as “low” speed versus “high” speed blending as follows. The Model7010G blender was connected to a Staco Energy Variable Transformer(Model number 3PN1010B), and the blender speed was adjusted by changingthe setting on the Transformer. In the examples and specification, “lowspeed” blending was achieved by setting the Transformer between 0 to 50,while “high speed” blending was achieved by setting the Transformerbetween 50 to 100.

Conductivity was measured using a Eutech PCSTestr 35 or a RadiometerAnalytical conductivity meter and measurements were according to theinstrument instruction manual and the references provided with eachinstrument. The solution or slurry pH measurements were made using aEutech PCSTestr 35 or Beckmann 0 265 laboratory pH meter.

Deionized water referred to herein as Milli-Q® water was obtained byinitially pretreating water using a Prepak 1 Pretreatment Pack, and thenfurther purifying the water using a Millipore Milli-Q® Advantage A10Water Purification System. This water was typically used within 2 hoursof collection.

Hexane, heptane, toluene and dichloromethane were dried over activatedmolecular sieves and degassed with nitrogen prior to use. Instrumentgrade isobutane, used as solvent for the ethylene homopolymerizationswas purchased from Airgas and purified by passage through columns ofactivated charcoal, alumina, 13X molecular sieves, and finally anOxyClear™ gas purifier Model No. RGP-R1-500, from Diamond Tool and Die,Inc. Ultra-high purity grade ethylene and hydrogen were obtained fromAirgas. The UHP (ultra-high purity) ethylene was further purified bypassage through columns of activated charcoal, alumina, 13X molecularsieves, and an OxyClear™ gas purifier Model No. RGP-R1-500. The UHPhydrogen was purified by passage through an OxyClear™ gas purifier ModelNo. RGP-R1-500. Purified propylene was obtained as a slip stream from acommercial polypropylene plant.

All preparations involving the handling of organometallic compounds werecarried out under a nitrogen (N₂) atmosphere using Schlenk techniques orin a glove box.

Zeta Potential Measurements

Zeta potentials of the colloidal suspensions disclosed herein werederived from measuring the electroacoustic effect upon application ofelectric field across the suspension. The apparatus used to performthese measurements was a Colloidal Dynamics Zetaprobe Analyzer™. Forexample, zeta potential measurements were used to determine thedispersed clay concentration in a 0.5 wt. % to 1 wt. % Volclay®HPM-20/water dispersion as follows. A 250 g to 300 g sample of thedispersion to be measured was transferred to the measurement vesselcontaining an axial bottom stirrer. The stirring speed was set fastenough to prevent settling or substantial settling of the dispersion butslow enough to allow the electroacoustic probe to be fully immersed inthe mixture when fully lowered. Typically the stirring speed was setbetween 250 rpm and 350 rpm, most often 300 rpm.

The Colloidal Dynamic Zetaprobe Analyzer™ measurement parameters usedwere the following: 5 readings at 1 reading/minute; particle density of2.6 g/cc; dielectric constant of 4.5. An initial estimated colloidalweight percentage of 0.7 wt. % to 1.0 wt. % (conc_(estimate)) wastypically entered into the Zetaprobe Analyzer™ software. Measuring a 5wt. % Volclay® HPM-20/water dispersion provided a zeta potential of −46mV. If the final dispersed clay concentration is referred to as “conc”in the equation below, then the final dispersed clay concentration canbe calculated from the initial estimated concentration according to thefollowing formula.

conc=conc_(estimate)*(measured zeta potential/(−46))

The Zetaprobe Analyzer™ was also used to dynamically track evolving zetapotential during titrations of clay dispersions with either colloidaldispersions or non-colloidal solutions. Typically, the cationicpolymetallate titrant (or other cationic titrant) was added to a 0.5 wt.% to 5.0 wt. % Volclay® HPM-20/water dispersion at 0.25 mL to 2.0 mL pertitration point, with an equilibration delay of from 30 seconds to 120seconds.

The Zetaprobe software calculates zeta potential using a colloidalparticle weight percentage which does not factor in the colloidaltitrant. Thus, in cases where the titrant is a colloidal species, themeasured zeta potential was adjusted to reflect the extra colloidalcontent of the measured solution through the following method.Initially, both the weight of the titrand clay and the titrant cationicspecies were determined by the following equations (where * indicatesmultiplication, W is weight, V is volume).

W _(titrant) =V _(titrant)*density_(titrant)solids %_(titrant)

W _(clay) =V _(total)*density_(titrand)*particleconcentration_(measured)

The density for 5% Volclay® HPM-20 aqueous dispersion (titrand) wasdetermined to be approximately 1.03 g/mL. The titrant weight was scaledaccording to its particle density relative to the particle density ofthe titrand Volclay® HPM-20 (montmorillonite), to provide an effectivetitrant weight (W_(efftitrant)), which in this example was calculated asfollows.

W _(efftitrant) =W _(titrant)*particle density_(titrant)/particledensity_(titrand)

The effective colloidal particle weight percentage (wt. %_(eff)) wasthen calculated, to provide an estimate of the relative increase incolloidal content compared to an equivalent titration using anon-colloidal titrant. The inverse of this value was then multiplied bythe measured zeta potential to determine an adjusted zeta potential asfollows.

wt. %_(eff)=(W _(efftitrant) +W _(clay))/V _(t)

A=wt. %_(measured)/wt. %_(eff)

ZP _(adjusted=) ZP _(measured) *A

During a zeta potential titrations of clay dispersions with a cationicpolymetallate, such as the titration of Volclay® HPM-20 montmorillonitewith aluminum chlorhydrate (ACH), the zeta potential was measured beforeand during the titration as a function of the titrant volume and themmol Al/g clay. Samples of the solid material formed at various pointsduring the titration were collected (for example, at 0 mmol Al/g clay,1.17 mmol Al/g clay, 1.52 mmol Al/g clay, and so forth), and each samplewas dried, calcined, and analyzed by powder XRD (x-ray diffraction).

As an example of the zeta potential titrations, FIG. 3 plots the zetapotentials of the series of dispersions provided by the titration ofVolclay® HPM-20 montmorillonite with aluminum chlorhydrate (ACH),plotting titrant volume versus zeta potential (mV) of the dispersion,and FIG. 4 plots the mmol Al/g clay versus zeta potential (mV) of thedispersion for the same titration. FIG. 2 provides a powder XRD patternof a series of calcined products collected from during this zetapotential titration of HPM-20 clay with ACH.

Powder X-Ray Diffraction (XRD) Studies

Powder X-ray patterns of clays and clay heteroadducts were obtainedusing standard X-ray powder diffraction techniques on a Bruker D8daVinci instrument, with a Bragg Brentano geometry with a “theta-theta”scan type, using a Back-loading holder with zero background Siliconchip. The detector used was a Linear Silicon Strip (LynxEYE) PSDdetector. The test sample was placed in the sample holder of a twocircle goniometer, enclosed in a radiation safety enclosure. The X-raysource was a 2.0 kW Cu X-ray tube, maintained at an operating current of40 kV and 25 mA. The X-ray optics were the standard Bragg-Brentanopara-focusing mode with the X-ray diverging from a DS slit (0.6 mm) atthe tube to strike the sample and then converging at a positionsensitive X-ray Detector (Lynx-Eye, Bruker-AXS). The two-circle 250 mmdiameter goniometer was computer controlled with independent steppermotors and optical encoders. Flat compressed powder samples were scannedat 0.8° (2θ) per minute (2-30°2θ over 35 minutes). The software suitefor data collection and evaluation was Windows based. Data collectionwas automated using the COMMANDER program by employing a BSML file, anddata was analyzed by the program DIFFRAC.EVA.

The XRD test method applied to the calcined clay heteroadducts disclosedherein for determining basal spacing is described in, for example, byMcCauley in U.S. Pat. No. 5,202,295 (for example, at column 27, lines22-43). Bragg's equation or law as applied to clays is nλ=2d·sin θ,wherein n is the repeat number, λ is 1.5418, d is d001 spacing and θ isthe angle of incidence.

Pore Volume and Pore Volume Distribution

Pore volumes of the clay heteroadducts are reported as the cumulativevolume in cc/g (cm³/g, cubic centimeters per gram) of all poresdiscernable by nitrogen desorption methods. For catalyst support orcarrier particles such as alumina powder, and for the clays and clayheteroadducts of this disclosure, the pore diameter distribution andpore volumes were calculated with reference to nitrogen desorptionisotherm (assuming cylindrical pores) by the B.E.T. (or BET) techniqueas described by S. Brunauer, P. Emmett, and E. Teller in the J. Am.Chem. Soc., 1939, 60, 309; see also ASTM D 3037, which identifies theprocedure for determining the surface area using the nitrogen BETmethod.

The pore volume distribution can be useful in understanding catalystperformance, and the pore volume (total pore volume), various attributesof pore volume distribution such as the percentage of pores in varioussize ranges, as well as “pore mode”, which describes the pore diameterscorresponding to local maxima in the dV(log D) vs. pore diameterdistribution, were derived from nitrogen adsorption-desorption isothermsbased on the method described by E. P. Barrett, L. G. Joyner and P. P.Halenda (“BJH”), in “The Determination of Pore Volume and AreaDistributions in Porous Substances. I. Computations from NitrogenIsotherms,” J. Am. Chem. Soc., 1951, 73 (1), pp 373-380.

Surface Area

Surface area was determined by nitrogen adsorption methods using thenitrogen adsorption-desorption isotherm using the B.E.T. (or BET)technique as described by S. Brunauer, P. Emmett, and E. Teller in theJ. Am. Chem. Soc., 1939, 60, 309; see also ASTM D 3037, which identifiesthe procedure for determining the surface area using the nitrogen BETmethod. All morphological properties involving weight, such as porevolume (PV) (cc/g, cubic centimeters per gram) or surface area (SA)(m²/g, meters squared per gram) were normalized to a “metals-free basis”in accordance with procedures well-known in the art. However, unlessstated otherwise, the morphological properties reported herein are on an“as-measured” basis without correcting for metals content.

Polymerization Reactions

Homo-polymerization of ethylene was conducted in a dry, 2 L stainlesssteel Parr autoclave reactor using 1 L of isobutane diluent. Table 3Areports properties and polymerization data for comparative supports andinventive heterocoagulated clay supports, using(1-n-butyl-3-methyl-cyclopentadienyl)₂ZrCl₂ and triethylaluminum (AlEt₃)as metallocene and co-catalyst. The selected pressure and temperature inthe reactor for calculating activities reported in Table 3A were 450total psi and 90° C., which were maintained electronically by anethylene mass flow controller, or alternatively, manually using ajacketed temperature controller. Table 3B reports surface area andporosity properties of comparative supports and inventiveheterocoagulated clay supports.

Polymerization data using the support-activators of this disclosurealong with polymerization data using comparative catalyst systems arepresented in Table 3A. The polymerization runs are labelled P1 throughP39, and the specific Example number of the support used in eachpolymerization run is listed.

When using hydrogen, a pre-mixed gas feed tank of purified hydrogen andethylene were used to maintain the desired total reactor pressure, witha high enough pressure in the feed tank so as not to significantlychange the ratio of ethylene-to-hydrogen in the feed to the reactor. Theaddition of hydrogen can affect the melt index of the polymer obtainedwith any given catalyst.

Prior to conducting a polymerization run, moisture was first removedfrom the reactor interior by pre-heating the reactor to at least 115° C.under a dry nitrogen flow, which was maintained for at least 15 minutes.Stirring was provided by an impellor and Magnadrive™ with a set pointof, for example, 600 rpm. The metallocene catalyst for thepolymerization runs of Table 3A was(1-n-butyl-3-methyl-cyclopentadienyl)₂ZrCl₂ and using triethylaluminum(AlEt₃ or TEA) as a co-catalyst or alkylating agent, with 1.8 mmol ofAlEt₃ (3 mL of 0.6 M solution of TEA in hexanes) typically being usedfor the polymerization runs in this table. The post-contacted catalystcomponents, that is the composition containing all the listed catalystsystem components that were previously contacted to form thecomposition, were prepared in an inert atmosphere glove box andtransferred to a catalyst charge tube or vessel. The catalyst chargevessel contents were then charged to the reactor by flushing them inwith 1 L of isobutane. The reactor temperature control system was thenturned on and is allowed to reach a few degrees lower than thetemperature set-point, which typically took about 7 minutes. The reactorwas brought to run pressure by opening a manual feed valve for theethylene, and polymerization runs were continued for the times reportedin Table 3A, for example, for 30 minutes or 60 minutes.

TABLE 3A Properties and polymerization data for comparative supports andinventive heterocoagulated clay supports. The polymerizations wereperformed at 450 psi reactor pressure and 90° C., using(1-n-butyl-3-methyl-cyclopentadienyl)₂ZrCl₂ and triethylaluminum (AlEt₃)as metallocene and co-catalyst.^(A) Solid isolation Recipe Effectivemethod Support- Polymer- Polymer- Support Ratio zeta filtration oractivator ization PE ization Example (mmol Al/ potential centrifugationcharge MCN time yield Activity Run no. No. g day) mV (number) (mg)(mmol) (min) (g PE) (g/g/h) P1 1 0.00 −46 None 76 0.0046 30 4 116 P2 20.00 −46 none 75 0.0092 30 34 917 P3 3 0.00 −46 none 75 0.0092 30 17 453P4 5 6.40 >80 centrifuge (m) 75 0.0092 30 126 3347 P5 6 6.36 >80centrifuge (m) 50 0.0046 60 162 3240 P6 7 6.40 >80 centrifuge (m) 200.0046 60 70 3500 P7 7 6.40 >80 centrifuge (m) 76 0.0092 30 176 4650 P87 6.40 >80 centrifuge (m) 75 0.0092 30 170 4544 P9 13 6.35 centrifuge(m) 75 0.0092 30 184 4907 Inventive P10 14 1.76 20 none 75 0.0092 30 0.924 P11 15 1.76 20 none 75 0.0092 30 1.3 35 P12 16 1.76 20 filtration (3)75 0.0092 30 38 1013 P13 16 1.76 20 filtration (3) 75 0.0092 30 50 1323P14 17 1.76 20 filtration (1) 75 0.0092 30 138 3680 P15 18 1.76 20filtration (1) 75 0.0092 30 177 4720 Comparative P16 19 0.30 −46filtration (1), 75 0.0092 30 11 293 centrifuge Inventive P17 20 1.17 −20filtration (2) 51 0.0046 60 193 3808 P18 20 1.17 −20 filtration (2) 350.0046 60 183 5225 P19 21 1.52 0 filtration (2) 35 0.0046 60 240 6857Comparative P20 22 2.50 70 filtration (1) 75 0.0092 30 138 3688 P21 232.50 70 filtration (2) 75 0.0092 30 156 4155 P23 24 3.50 86 filtration(1) 75 0.0092 30 135 3581 P24 25 3.50 86 filtration (2) 75 0.0092 30 1333547 P25 26 0.30 −46 filtration (1), 75 0.0092 30 8 213 centrifuge P2627 0.60 −38 filtration (1) 75 0.0092 30 44 1181 Inventive P27 28 1.52 0filtration (3) 75 0.0092 30 105 2808 P28 29 1.52 0 filtration (1) 750.0092 30 114 3027 P29 30 1.76 20 filtration (1) 75 0.0092 30 157 4173P30 31 1.52 −9 filtration (1) 75 0.0092 30 114 3040 Comparative P31 322.50 38 filtration (1) 75 0.0092 30 143 3813 P32 33 0.50 −34 filtration(1) 75 0.0092 30 99 2637 Inventive P33 34 1.01 0 filtration (1) 750.0092 30 100 2653 Comparative P34 35 1.46 68 filtration (1) 75 0.009230 108 2880 Inventive P37 36 4.80 −20 filtration (1) 75 0.0092 30 481288 P39 39 3.31 20 filtration (3) 75 0.0092 30 52 1376^(A)Abbreviations: MCN, metallocene; PE, polyethylene.

TABLE 3B Surface area and porosity properties of comparative supportsand inventive heterocoagulated clay supports.^(A) Cumulative CumulativeDVlogDmax dV(logD)max Effective BET BJH BJH % of total 30-40 max/200-500 max/ Polymer- Support zeta surface BJH porosity porosity 2-meso. DvlogD200- dV(logD)60- ization Example potential area Porosity3-10 nm 30 nm porosity in V(10-30 nm)/ 500 max 200 max Run no. No. mV(m²/g) (cc/g) (cc/g) (cc/g) 3-10 nm V(3-10 nm) <2 >1 P1 1 −46 9 0.060.036 0.05 73 0.37 15.07  0.81 P2 2 −46 22 0.175 0.026 0.08 30 2.29 2.071.09 P3 3 −46 34.5 0.2 0.079 0.14 58 0.72 — — P4 5 >80 286 0.365 0.0360.11 33 2.04 0.98 0.10 P5 6 >80 296 0.57 0.077 0.18 43 1.34 — — P6 7 >80247 1.104 0.060 0.22 27 2.69 0.42 1.31 P7 7 >80 247 1.104 0.060 0.22 272.69 0.42 1.31 P8 7 >80 247 1.104 0.060 0.22 27 2.69 0.42 1.31 P9 13 2390.812 0.054 0.21 26 2.85 0.49 2.24 Inventive P10 14 20 1 0.014 0.0010.01 17 4.80 1.60 1.13 P11 15 20 2.5 0.015 0.003 0.01 42 1.35 — — P12 1620 NA 0.112 0.078 0.09 83 0.21 19.62  0.85 P13 16 20 NA 0.112 0.078 0.0983 0.21 19.62  0.85 P14 17 20 295 0.531 0.044 0.12 37 1.68 1.05 18.26 P15 18 20 212 0.544 0.050 0.15 32 2.08 1.04 2.14 Comparative P16 19 −4656 0.472 0.042 0.24 18 4.71 0.54 2.02 Inventive P17 20 −20 104 0.5920.032 0.17 19 4.38 0.66 2.27 P18 20 −20 104 0.592 0.032 0.17 19 4.380.66 2.27 P19 21 0 132 0.261 0.040 0.12 33 1.99 2.05 1.82 ComparativeP20 22 70 224 0.661 0.042 0.14 30 2.29 0.83 1.85 P21 23 70 275 0.7220.047 0.16 29 2.45 0.88 1.99 P23 24 86 289 1.457 0.054 0.21 25 2.96 0.452.12 P24 25 86 280 0.724 0.043 0.16 26 2.79 0.80 2.29 P25 26 −46 270.169 0.107 0.15 73 0.37 9.68 0.79 P26 27 −38 41 0.351 0.051 0.13 401.49 2.22 1.68 Inventive P27 28 0 139 0.439 0.038 0.13 28 2.53 1.09 1.76P28 29 0 122 0.536 0.039 0.13 31 2.21 1.01 1.81 P29 30 20 187 0.5980.040 0.12 33 1.99 0.86 1.83 P30 31 −9 148 0.457 0.028 0.10 29 2.43 0.911.99 Comparative P31 32 38 219 0.45 0.055 0.12 46 1.19 1.67 1.68 P32 33−34 28 0.383 0.046 0.12 38 1.63 0.85 1.92 Inventive P33 34 0 22 0.350.017 0.07 23 3.37 0.38 1.99 Comparative P34 35 68 44 0.432 0.022 0.0829 2.46 0.94 1.82 Inventive P37 36 −20 NA NA 0.294 0.58 51 0.96 0.120.58 P39 39 20 113 1.58 0.027 0.35 8 12.06 0.07 3.33 ^(A)Abbreviations:NA, not available; DVlogDmax30-40 max/DvlogD200-500 max, alsoabbreviated D_(VM(30-40))/D_(VM(200-500)), is the ratio of the maximumvalue of dV(log D) between 30 Å and 40 Å and the maximum value of dV(logD) between 200 Å and 500 Å; and DVlogDmax200-500 max/DvlogD60-200 max,also abbreviated D_(VM(200-500))/D_(VM(60-200)), is the ratio of themaximum value of dV(log D) between 200 Å and 500 Å and the maximum valueof dV(log D) between 60 Å and 200 Å.

Alternatively, the contents of the catalyst charge tube can be pushedinto the reaction vessel with ethylene at several degrees below the setpoint temperature of the run, for example, about 10 degrees centigradebelow the set point temperature. In this method, two charge tubes wereused. When the run pressure was reached, the reactor pressure wascontrolled by the mass flow controller. The consumption of ethylene andthe temperature were monitored electronically. During the course of thepolymerization, with the exception of the initial charge of catalystduring the first few minutes of the run, the reactor temperature wasmaintained at the set point temperature ±2° C. After 60 minutes or afterthe designated run time, the polymerization was stopped by shutting offthe ethylene inlet valve and venting the isobutane. The reactor wasreturned to ambient temperature. The polymer produced in the reactionwas then removed from the reactor and dried, and the polymer weight wasused to calculate the activity of the particular polymerization. Polymermelt indices, specifically, melt index (MI) and high load melt index(HLMI), were obtained after stabilization of the polymer with butylatedhydroxytoluene (BHT) according to ASTM procedures D618-05 and D1238-04C.Polymer density was measured according to ASTM D1505-03.

Catalyst and Polymer Characterization

The ¹H NMR spectra of metallocene compounds were collected at roomtemperature by placing 20 mg of the metallocene sample into a 10 mm NMRtube, to which 3.0 mL of CDCl₃ were added. ¹H NMR spectra were acquiredon a Bruker AVANCE™ 400 NMR (400.13 MHz). Chemical shifts are reportedin ppm (δ) relative to TMS, or referenced to the chemical shifts ofresidual solvent proton resonances. Coupling constants are reported inHertz (Hz).

The NMR determination of isotactic pentads content in the polypropylenewas obtained by place 400 mg of polymer sample into a 10 mm NMR tube,into which 1.7 g of tetracholoroethane-d2 and 1.7 g of o-dichlorobenzenewere added. The ¹³C NMR spectra were acquired on a Bruker AVANCE™ 400NMR (100.61 MHz, 90° pulse, 12 s delay between pulse). About 5000transients were stored for each spectrum, and the mmmm pentad peak(21.09 ppm) was used as reference. The microstructure analysis wascarried out as described by Busico, et al., Macromolecules, 1994, 27,4521-4524.

The polypropylene Melt Flow Rate (MFR) was determined at 230° C. underthe load of 2.16 kg according to ASTM D-1238 procedure.

Polypropylene melting temperature Tm was obtained according to ASTMD-3417 procedure using DSC and TA Instrument, Inc. Model: DSC Q1000.

Nitrogen adsorption-desorption data for the support-activators and othermaterials were collected using an Anton Paar Autosorb iQ apparatus. Arepresentative measurement was carried out as follows. A 50 mg to 150 mgcalcined sample was weighed into a sample cell under an inert atmosphereand sealed with a stopper. The sample cell was inserted into theAutosorb iQ station and placed under vacuum. The sample was subsequentlycooled using liquid nitrogen. The nitrogen adsorption-desorptionisotherms were recorded at 77 K and from relative pressures P/P₀=0.05 to1 (P₀=atmospheric pressure).

Example 1 Comparative Example of the Preparation of a Calcined Clay

A 700 mg sample of Volclay® HPM-20 clay in the form of the as-receivedpowder was combined with 60 mL of deionized water. The mixture wasagitated vigorously and was rotary evaporated for 20-30 minutes at 55°C. The resulting sample was then calcined for 6 hours at 300° C. toafford 620 mg of a grey powder. The nitrogen adsorption/desorption BJHpore volume analysis is plotted in FIG. 12.

Example 2 Comparative Example of the Preparation of an Azeotroped Clay

A 5.16 g sample of Volclay® HPM-20 clay powder was placed in around-bottom flask and combined with 40 mL to 60 mL of n-butyl alcohol.This mixture was agitated vigorously and was then rotary evaporated at45° C. to dry. This drying step was stopped shortly after the alcoholwas visibly evaporated. The odor of n-butyl alcohol was typicallynoticeable from the sample after this process. A 5.39 g sample of wetclay was obtained, and 4.46 g of this material was then calcined for 6hours at 300° C. to afford 3.3 g of a black powder.

Example 3 Comparative Example of the Preparation of a Sheared, thenAzeotroped Clay

A 133 g sample of a 5 wt. % HPM-20/water dispersion, prepared by slowlyadding with stirring the HPM-20 clay to deionized water in a Waring®blender, was initially rotary evaporated at 45° C. to 55° C. to removemost of the water content, after which 50 mL of n-butanol was thenadded. Rotary evaporation at 45° C. was continued, and drying wasstopped shortly after the alcohol had visibly evaporated. A 3.2 g sampleof this material was then calcined for 6 hours at 300° C. to afford 2.6g of a grey powder. The BJH pore volume analysis of this material isprovided in FIG. 11.

Example 4 Preparation of Colloidal Clay Dispersion

To a Waring® blender was charged 570 g of deionized water, and withstirring, 30.0 grams of HPM-20 was added portion-wise. This mixture wasstirred at a high rate (revolutions per minute, rpm) to afford asubstantially lump or clump-free dispersion 5 wt. % dispersion of HPM-20suspension. When a 4.8 wt. % dispersion of Volclay® HPM-20 clay wasprepared using 20 g of HPM-20 and 394 g of water and stirred using aWaring® blender at high rpm to afford a clump-free dispersion, thedispersion was characterized by a conductivity of 908 μS/cm and pH of9.39.

Example 5 Comparative Example of the Preparation of AluminumChlorhydrate (Al₁₃ Keggin-Ion)-Pillared Clay Using Aluminum ChlorhydrateSolution (6.4 mmol Al/g Clay)

A Waring® blender was charged with 100 g of the colloidal claydispersion prepared according to Example 4, followed by, with stirring,6.9 g of 50% GEO aluminum chlorhydrate solution with reported basicityof 83.47%. After addition of the aluminum chlorhydrate, the mixture wasstirred at high a high rate (rpm) for an additional 3 minutes. The pH ofthe mixture was measured as pH 4.23. Attempts to filter the resultingmixture through Fisherbrand™ P8 filter paper were unsuccessful.Therefore, two aliquots of the mixture were transferred to 50 milliliterplastic centrifuge tubes, and the samples were centrifuged for a totalof 140 minutes at 3600 rpm on a Beckmann Coulter Allegra 6 centrifuge.The resulting clear supernatant was decanted off each tube and replacedwith deionized water. The samples were shaken to re-suspend the solidsand centrifuged again. This process was repeated multiple times(typically 4 to 8 times) until the supernatant of one centrifuged sampleafforded a conductivity of 67 μS/cm and a pH of 6.0. The supernatant wasthen decanted and a minimum of deionized water was used to transfer thesolids to an Erlenmeyer flask along with approximately 70 mL ofn-butanol. Rotary evaporation afforded 2.11 g of off-white powder. A 437mg sample of this powder was charged to porcelain bowl and placed in an300° C. oven for 6 hours to afford 0.301 grams of a dark grey powder.

Example 6 Reproducibility of the Preparation of Aluminum Chlorhydrate(Al₁₃ Keggin-ion)-Pillared Clay Using Aluminum Chlorhydrate Solution(6.4 mmol Al/g Clay):

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After this addition was complete, the resulting dispersion was blendedat high speed for 5 to 10 minutes to obtain a slightly viscous mixtureof 5 wt. % aqueous dispersion of the HPM-20 clay.

A 150 g portion of this 5 wt. % aqueous dispersion of HPM-20 wastransferred into a Waring® blender, and 9.35 g of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture was blended at highspeed for 5 minutes, then portioned into four 50 mL centrifuge tubes andcentrifuged at 3000 rpm to 3500 rpm for 30 to 60 minutes. Thesupernatant pH and conductivity were measured (Eutech PCSTestr 35). Thesupernatant was decanted and the remaining wet solid was re-suspended indeionized Milli-Q® water. The centrifugation process (centrifuge,supernatant pH/conductivity measurement, supernatant removal, andre-suspension in deionized Milli-Q® water) was repeated until theconductivity of the supernatant reached 100 to 300 μS/cm. In total, sixcentrifugations were performed, at which point the supernatant wasdiscarded for a final time. To the remaining wet solid was added 200 mLof 1-butanol, which after rotary evaporation at 45° C. yielded 9.75 g ofwet solid. This wet solid was then ground with a pestle and mortar, 4.28g of this solid were transferred to a porcelain crucible and werecalcined for 6 hours at 300° C. to afford 1.65 g of a grey-black powder.

Example 7 Comparative Example of the Preparation of AluminumChlorhydrate (Al₁₃ Keggin-Ion)-Pillared Clay Using Powdered AluminumChlorhydrate (6.4 mg Al/g Clay)

With stirring, a 30 g sample of HPM-20 clay was added slowly over thecourse of 1 to 2 minutes into a Waring® blender containing 570 g ofdeionized Milli-Q® water, while stirring at low speed, which afforded agrey colloidal dispersion containing no, or substantially no visiblelumps or clumps. After the addition was complete, the dispersion wasblended at high speed for 5 to10 minutes to obtain a slightly viscousmixture of 5 wt. % aqueous dispersion of the HPM-20 clay.

A 100 g sample of this 5 wt. % HPM-20 aqueous dispersion was transferredinto a Waring® blender, and 3.42 g of Parchem ALOXICOLL® 51P powder wasweighed into a vial and diluted with 35 to 40 g deionized Milli-Q® waterand was then added all at once to the dispersion. The mixture wasblended at high speed for 5 minutes, then portioned into four 50 mLcentrifuge tubes and centrifuged at 3000 to 3500 rpm for 30 to 60minutes. The supernatant pH and conductivity were measured (EutechPCSTestr 35). The supernatant was decanted and the remaining wet solidwas re-suspended in deionized Milli-Q® water. The centrifugation process(centrifuge, supernatant pH/conductivity measurement, supernatantremoval, and re-suspension in deionized Milli-Q® water) was repeateduntil the conductivity of the supernatant reached 100 to 300 μS/cm (intotal, six centrifugations were performed, with final supernatant pH of4.25 and conductivity of 225 μS/cm), at which point the supernatant wasdiscarded for a final time. The remaining wet solid was combined with100 to 200 mL of 1-butanol in a round-bottom flask and rotary evaporatedat 45° C. to afford 5.54 g of wet solid, which was then ground with apestle and mortar. A 1.8 g portion of this solid was transferred to aporcelain crucible and calcined for 6 hours at 300° C. to afford 1.2 gof a grey-black powder.

Example 8 Gravimetric Determination of the Colloidal Clay Content of 1%Aqueous Volclay® HPM-20 Dispersions

A 60 g sample of a 5 wt. % HPM-20 clay dispersion in water was combinedwith 240 g of Milli-Q® deionized water to give 300 g of a 1 wt. % HPM-20aqueous dispersion. Upon standing for a time period of from 30 minutesto an hour, a significant amount of settled clay was observed in thisdiluted dispersion. The colloidal portion was decanted off, and thesettled portion was collected, dried and weighed. This process provided900 mg of HPM-20 clay which was collected, corresponding to a 0.7%colloidal content for the diluted dispersion. In repetitions of thisexperiment using between 280 to 290 g of this 1% HPM-20 dispersion, 630mg and 910 mg of solid clay was isolated, respectively, resultingcolloidal content values of 0.77 and 0.69 wt. % for the diluteddispersions.

Example 9 Zeta Potential Determination of Aluminum Chlorhydrate/Volclay®HPM-20 Ratio in a Clay Heteroadduct

With stirring, 30 g of HPM-20 clay was added slowly over the course of afew minutes into a Waring® blender containing 570 g of Milli-Q®deionized water to afford a grey colloidal dispersion containing no, orsubstantially no, visible lumps or clumps. After the addition wascomplete, the dispersion was stirred at high speed for 5 to 10 minutesto obtain a slightly viscous mixture of 5 wt. % aqueous dispersion ofHPM-20 clay. A 42 g portion of this 5 wt. % HPM-20 aqueous dispersionwas combined with 258 g of Milli-Q® deionized water to give a 0.7 wt. %HPM-20 aqueous dispersion. Then, 280 g of this 0.7 wt. % colloidaldispersion was transferred to the measurement vessel of a ColloidalDynamics Zetaprobe Analyzer™, containing an axial bottom stirrer. Thestirring speed was set between 250 rpm and 350 rpm.

In accordance with the procedure outlined in the Colloidal DynamicsZetaprobe Analyzer™ manual supplied with the instrument, a zetapotential measurement was performed on this diluted HPM-20 aqueousdispersion using an initial colloidal content estimate of 0.7 wt. % todetermine the actual colloidal content of the clay dispersion. Measuringa 5 wt. % HPM-20 aqueous dispersion results in a zeta potentialmeasurement of −46 mV (negative 46 millivolts). The initial colloidalcontent estimate was adjusted to match this zeta potential. In thisinstance, the HPM-20 colloidal content of the dispersion was determinedto be 0.62%. Colloidal Dynamic Zetaprobe measurement parameters were asfollows: 5 readings, 1 reading/minute; particle density of 2.6 g/cc;dielectric constant of 4.5.

A 2.5 wt. % aqueous solution of aluminum chlorohydrate (ACH) wasobtained through dilution of a 50 wt. % aluminum chlorohydrate solution(GEO). A volumetric titration of this 2.5 wt. % ACH solution into the0.7 wt. % HPM-20 aqueous dispersion was then performed. Titrationsettings were 0.5 mL per titration point, with an equilibration delay of30 seconds, that is, following the addition of 0.5 mL of the aqueous ACHsolution, a 30 second delay to allow for equilibration was taken priorto the zeta potential measurement.

FIG. 3 and Table 4 report the results of this zeta potential titrationfor the volumetric addition of the 2.5 wt. % aqueous solution ofaluminum chlorohydrate (ACH) into the 0.7 wt. % HPM-20 aqueousdispersion, plotting the measured zeta potential versus the titrantvolume (mL). The titrant volume indicates the cumulative volume of theaqueous aluminum chlorohydrate solution added. Based on the amount ofACH solution and the measured density of 1.075 g/mL for the ACHsolution, and ACH molar aluminum/clay mass ratios used to achieve −20mV, neutral, and +20 mV zeta potential are summarized in Table 4.

TABLE 4 Results for zeta potential titration of ACH into Volclay ®HPM-20 aqueous dispersion Cumulative ACH volume of 2.5 Al molar wt. %ACH content/g in aqueous Volclay ® Zeta potential solution (mL) HPM-20−20 mV  9.3 1.17 mmol Al/g clay  0 mV 12.1  1.52 mmol Al/g clay +20 mV 14.05 1.73 mmol Al/g clay

Example 10 Zeta Potential Determination of Polyaluminum ChlorideUltraPAC® 290/Volclay® HPM-20 Ratio in a Clay Heteroadduct

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of Milli-Q®deionized water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was stirred by blendingat high speed for 5 to 10 minutes to obtain a slightly viscous mixtureof 5 wt. % aqueous dispersion of HPM-20 clay.

A 60 g portion of this 5 wt. % HPM-20 aqueous dispersion was combinedwith 240 g of Milli-Q® deionized water to give a 1 wt. % HPM-20 aqueousdispersion. Approximately 280 g of this 1 wt. % colloidal dispersion wastransferred to the measurement vessel of a Colloidal Dynamics ZetaprobeAnalyzer™, containing an axial bottom stirrer. The stirring speed wasset as described above.

A zeta potential measurement was performed on this diluted HPM-20aqueous dispersion using an initial colloidal content estimate of 1 wt.% to determine the actual colloidal content of the clay dispersion.Measuring a 5 wt. % HPM-20 aqueous dispersion results in a zetapotential of −46 mV. The initial colloidal content estimate is adjustedto match this zeta potential. In this instance, the HPM-20 claycolloidal content of the dispersion was estimated to be 0.67%. ColloidalDynamic Zetaprobe Measurement parameters were the following: 5 readings,1 reading/minute; particle density of 2.6 g/cc; dielectric constant of4.5.

A 4.58 g sample of polyaluminum chloride (abbreviated “PAC”) UltraPAC®290 (17.1% Al₂O₃ content) was diluted into a 100 mL volumetric flaskusing Milli-Q® deionized water. A volumetric titration of this 4.58 wt.% UltraPAC® 290 solution into the aforementioned 1 wt. % HPM-20 claydispersion was then performed. Titration settings were 1 mL pertitration point, with an equilibration delay of 30 seconds.

FIG. 5 and Table 5 report the results from these zeta potentialmeasurements, where titrant volume indicates the cumulative volume ofthe 4.58 wt. % aqueous UltraPAC® 290 solution added, plotting themeasured zeta potential versus the titrant volume (mL). The amount ofUltraPAC® 290 dispersion used to achieve −20 mV, neutral, and +20 mVzeta potential is summarized in Table 5.

TABLE 5 Results for zeta potential titration of UltraPAC ® 290 intoVolclay ® HPM-20 aqueous dispersion Cumulative Amount of PAC volume ofUltraPAC ® Al molar UltraPAC ® 290 dispersion content vs. 290 vs.Volclay ® Volclay ® Zeta potential (mL) HPM-20 (g/g) HPM-20 −20 mV  8.55 0.190 0.69 mmol Al/g clay  0 mV 13.1  0.291 1.06 mmol Al/g clay+20 mV  14.4  0.320 1.16 mmol Al/g clay

Example 11 Zeta Potential Determination of NYACOL® AL27 ColloidalAlumina/Volclay® HPM-20 Ratio in a Clay Heteroadduct

A 1 wt. % HPM-20 clay dispersion was prepared by addition ofapproximately 60 g of 5 wt. % HPM-20 aqueous dispersion into 240 g ofMilli-Q® water. A 285 g to 300 g portion of the 1 wt. % dispersion wastransferred to the measurement container of the Zetaprobe and an initialzeta potential measurement was taken to estimate the true particle wt. %of the solution.

A zeta potential measurement was performed on this diluted HPM-20aqueous dispersion to determine the actual colloidal content of the claydispersion. Measuring a 5 wt. % HPM-20 aqueous dispersion results in azeta potential of −44.2 mV. The initial colloidal content estimate isadjusted to match this zeta potential. In this instance, the HPM-20 claycolloidal content of the dispersion was determined to be 0.92%.Colloidal Dynamic Zetaprobe Measurement parameters were the following: 5readings, 1 reading/minute; particle density of 2.6 g/cc; dielectricconstant of 4.5.

A 100 g sample of commercial NYACOL® AL27 colloidal alumina dispersion(20 wt. % Al₂O₃) was combined with 100 g of Milli-Q® deionized water toafford a 10 wt. % Al₂O₃ dispersion of NYACOL® AL27. A volumetrictitration of this 10 wt. % dispersion into the aforementioned 1 wt. %HPM-20 clay dispersion was then performed. (The concentrationdesignation of 1 wt. % HPM-20 is based upon the recipe rather than azeta potential estimate which was determined to be about 0.92 wt. %,because not all of the clay was colloidal upon dilution.) Titrationsettings were as follows: 1 mL per titration point from 0 mL to 27 mL,and 3 mL per titration point afterwards, with an equilibration delay of60 seconds.

FIG. 6 and Table 6 report the results from these measurements, wheretitrant volume indicates the cumulative volume of the NYACOL® AL27alumina dispersion added. In this example, the titrant is also acolloidal species. The zeta potential is adjusted using the previouslydescribed method to provide the date in FIG. 6. The amount of NYACOL®AL27 dispersion used to achieve −20 mV, neutral, and +20 mV zetapotential is summarized in Table 6.

TABLE 6 Results for zeta potential titration of NYACOL ® AL27 colloidalalumina into Volclay ® HPM-20 Amount of NYACOL ® Amount of Al molar AL27Amount Al₂O₃ vs. content vs. dispersion vs. of titrant Volclay ®Volclay ® Volclay ® (10 wt. % HPM-20 HPM-20 HPM-20 Zeta potential Al₂O₃,mL) (g/g) (mmol/g) (g/g) −20 mV  11.5   0.486 4.8  2.43  0 mV 18    0.767.5 3.8 +20 mV  35.25  1.49 14.6   7.45

Example 12 Preparation of Aluminum Chlorhydrate Clay Heteroadduct (1.76mmol Al/g Clay)

A Waring® Blender was charged with 475.22 grams of deionized water. Withstirring, 25.09 grams of HPM-20 clay from American Colloid was addedslowly. After the clay addition was completed, the mixture was stirredfor 5 minutes on high to afford a homogeneous suspension with no lumps,after which 9.53 grams of aluminum chlorhydrate 50 wt. % aqueoussolution (GEO) was added with stirring, and stirred continued for 9minutes. The mixture was poured into a high density polyethylene bottle.The Waring® flask was rinsed with 42.5 grams of deionized Milli-Q®water, and the rinse water was transferred to the bottle. The bottle wasshaken to thoroughly mix the contents, and the conductivity of theslurry was measured as 4.03 mS/cm, and the pH was 5.89.

A second batch of the aluminum chlorhydrate clay heteroadduct wasprepared in the same fashion using 380.26 grams of deionized Milli-Q®water, 20.03 grams of HPM-20 clay, and 7.70 grams of aluminumchlorhydrate 50 wt. % aqueous solution (GEO). The conductivity of thisbatch was measured to be 3.64 mS/cm and the pH was 5.58. The contents ofthe second batch were transferred, along with 30 grams of deionizedwater to transfer residual slurry, to the bottle containing the firstbatch. The bottle was shaken to afford a grey slurry with no visiblelumps. The final conductivity of the combined batches was 3.84 mS/cm andthe final pH was 5.87.

Example 13 Comparative Example of the Preparation of an AluminumSesquichlorohydrate Clay Heteroadduct Using Powdered AluminumSesquichlorohydrate (ASCH, 6.4 mmol Al/g Clay)

In this comparative example, the synthesis of an aluminumsesquichlorohydrate clay heteroadduct using powdered aluminumsesquichlorohydrate (ASCH), which demonstrates the need to use multiplewashings and centrifugations in order to isolate the product, comparedto the procedures and products of Examples 31 and 32.

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial were charged 3.53g of ALOXICOLL® 31P powder and 35 to 40 mL of deionized Milli-Q® water,and this mixture was poured all at once into the stirred dispersion. Themixture was blended at high speed for 5 minutes, then portioned intofour 50 mL centrifuge tubes and centrifuged at 3000 rpm to 3500 rpm for30 to 60 minutes. The supernatant pH and conductivity were measured(Eutech PCSTestr 35), which provided a pH of 4.0 and a conductivity of7300 μS/cm. The supernatant was decanted and the remaining wet solid wasre-suspended in deionized Milli-Q® water. The centrifugation process(centrifuge, supernatant pH/conductivity measurement, supernatantremoval, and re-suspension in deionized Milli-Q® water) was repeateduntil the conductivity of the supernatant reached 100 to 300 μS/cm.Achieving this conductivity required, in total, six centrifugations tobe performed, with the final supernatant pH measured to be 4.3 and theconductivity measured to be 286 μS/cm. At this point, the supernatantwas discarded for a final time and the remaining wet solid was combinedwith 100 to 200 mL of 1-butanol in a round-bottom flask and rotaryevaporated at 45° C. to afford 5.82 g of wet solid, which was thenground with a pestle and mortar. A 2.1 g sample of this solid wastransferred to a porcelain crucible and calcined for 6 hours at 300° C.,to afford 1.1 g of a grey-black powder.

Example 14 Spray Drying, Screening, and Calcining Unwashed AluminumChlorhydrate Clay Heteroadduct Retained on a 325 Mesh Screen (1.76 mmolAl/g Clay)

A portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/gclay) mixture (slurry) prepared according to Example 12 was spray driedusing a Buchi B290 laboratory spray drier. Some of the spray-dried clayheteroadduct was screened through a 325 mesh screen. Two grams of thematerial retained on the 325 mesh screen were charged to a 300° C. ovenand heated for 6 hours in air. While still hot, the material wastransferred to a vacuum chamber and left to cool to room temperatureunder vacuum.

Example 15 Spray Drying, Screening, and Calcining Unwashed AluminumChlorhydrate Clay Heteroadduct Passing Through a 325 Mesh Screen (1.76mmol Al/g Clay)

A portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/gclay) mixture (slurry) prepared according to Example 12 was spray driedusing a Buchi B290 laboratory spray drier. Some of the spray-dried clayheteroadduct was screened through a 325 mesh screen. Two grams ofthrough-screen material were charged to a 300° C. oven and heated for 6hours in air. While still hot, the material was transferred to a vacuumchamber and left to cool to room temperature under vacuum.

Example 16 Spray Drying and Calcining Washed Aluminum Chlorhydrate ClayHeteroadduct (1.76 mmol Al/g Clay)

A portion of the aluminum chlorhydrate clay heteroadduct (1.76 mmol Al/gclay) slurry prepared according to Example 12 was filtered throughFisherbrand™ P8 filter paper using a Buchner funnel and vacuum. The 158gram filter cake was then transferred to a HDPE bottle and re-suspendedin about 1.2 liter of deionized water by shaking. The conductivity ofthe thus-obtained slurry was 114 μS/cm and the pH was 6.25. This slurrywas filtered again through Fisherbrand™ P8 filter paper and left onfilter under vacuum overnight to afford 109.03 grams of a grey solid. A97.07 gram sample of this solid was charged to a HDPE bottle along with452 g of deionized water and shaken until no lumps were visible in theslurry. The conductivity of this slurry was 112 μS/cm and the pH was6.33. A portion of this aluminum chlorhydrate clay heteroadduct slurrywas spray dried using a Buchi B290 laboratory spray drier. A 1.77 gramsample of the spray dried material was charged to a 300° C. oven for 6hours in air to calcine. While still hot, the material was thentransferred to a vacuum chamber and left to cool to room temperatureunder vacuum.

Example 17 Single Filtration, Azeotroping, and Calcining an AluminumChlorhydrate Clay Heteroadduct (1.76 mmol Al/g Clay)

A 543 gram portion of the aluminum chlorhydrate clay heteroadduct (1.76mmol Al/g clay) slurry prepared according to Example 12 was vacuumfiltered through Fisherbrand™ Brand P8 filter paper. The resultingfilter cake was then re-suspended in approximately 1 L of deionizedwater to afford a slurry with a conductivity of 114 μS and a pH of 6.25.This slurry was then vacuum filtered through Fisherbrand™ Brand P8paper, and 11.5 grams of the filter cake from the clay-heteroadductretained on the filter paper were charged to an Erlenmeyer flaskequipped with a stir bar. Then 200 mL of n-butanol was added and themixture stirred until a slurry with no visible lumps or clumps wasobtained. The stir bar was removed and the Erlenmeyer was rotaryevaporated from a 45° C. bath. The off-white powder containing someflakes and chunks was very gently ground to a uniform powder and 1.04grams were charged to a porcelain crucible that was calcined in air for6 hours at 300° C. The calcined material was cooled down under vacuumand 0.867 grams were transferred to an inert atmosphere glove box.

Example 18 Reproducibility of Single Filtration, Azeotroping, andCalcining an Aluminum Chlorhydrate Clay Heteroadduct (1.76 mmol Al/gClay) According to Example 17

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender, and 1.91 g of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture coagulated rapidly, and70 mL of deionized Milli-Q® water was added in order to facilitatestirring. The mixture was then blended at high speed for 5 minutes, andsubsequently vacuum filtered through Fisher P8 Qualitative-Grade FilterPaper (coarse porosity). After allowing 15 to 30 minutes for thefiltration, the filtrate pH and conductivity were measured (EutechPCSTestr 35), to provide a pH of 6.1 and a conductivity of 1516 μS/cm.The filtrate was discarded, and the remaining wet solid was re-suspendedin 50 to 100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, and filtrate pH/conductivity measurement) wasrepeated once more. The remaining wet solid was re-suspended in 150 to200 mL of 1-butanol and rotary evaporated at 45° C. The resulting solidwas then ground with a pestle and mortar to obtain 5.18 g of a lightgrey powder. A 1.90 g portion of this solid was transferred to aporcelain crucible and calcined for 6 hours at 300° C. to afford 0.9 gof a grey-black powder. The powder XRD (x-ray diffraction) pattern ofthis sample appears in FIG. 2, and the BJH pore volume analysis of thissample is plotted in FIG. 10.

Example 19 Comparative Example of the Preparation of AluminumChlorhydrate (ACH) Ion-Exchanged Clay (0.3 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 0.325 g sample of GEO ACH aqueousdispersion (50 wt. %) was pipetted into a vial and combined with 20 mLof deionized Milli-Q® water, which was then poured all at once into theclay dispersion. The resulting mixture was then blended at high speedfor 5 minutes, then vacuum filtered through Fisher P8 Qualitative-GradeFilter Paper (coarse porosity). Filtration was slow (<1 drop/second).After allowing 15 to 30 minutes for the filtration to proceed, thefiltrate pH and conductivity were measured (Eutech PCSTestr 35), whichprovided a pH of 7.3 and a conductivity of 487 μS/cm. The filtrate wasdiscarded, and the remaining wet solid was re-suspended in 50 mL ofdeionized Milli-Q® water and centrifuged once at 3000 rpm to 3500 rpmfor 30 to 60 minutes. After removing the supernatant (having a measuredconductivity of 180 μS/cm), the remaining wet solid was re-suspended in50 to 100 mL of 1-butanol and rotary evaporated at 45° C. The resultingsolid was then ground with a pestle and mortar, 1.7 g of the groundsolid was then transferred to a porcelain crucible and calcined for 6hours at 300° C. to afford 0.8 g of grey-black powder.

Example 20 Preparation of Aluminum Chlorhydrate (ACH)-Clay Heteroadduct(1.17 mmol Al/g Clay)

With stirring, 30 g of Volclay® HPM-20 clay was added slowly over thecourse of 1 to 2 minutes into a Waring® blender containing 570 g ofdeionized Milli-Q® water while stirring at low speed to afford a greycolloidal dispersion containing no, or substantially no visible lumps orclumps. After the addition was complete, the dispersion was blended athigh speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5wt. % aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. Then, 1.27 g of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture coagulated rapidly, and70 mL of deionized Milli-Q® water was added in order to facilitatestirring. The mixture was then blended at high speed for 5 minutes, andsubsequently vacuum filtered through Fisher P8 Qualitative-Grade FilterPaper (coarse porosity). After allowing 15 to 30 minutes for thefiltration, the filtrate pH and conductivity were measured (EutechPCSTestr 35), which provided a pH of 6.25 and a conductivity of 1166μS/cm. The filtrate was discarded and the remaining wet solid wasre-suspended in 50 to 100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, filtrate pH/conductivity measurement) wasrepeated until the conductivity of the re-suspended slurry reached 100to 300 μS/cm. In this case, one additional filtration was performed toobtain a slurry with a pH of 6.2 and a conductivity of 188 μS/cm. Theremaining wet solid was re-suspended in 150 to 200 mL of 1-butanol androtary evaporated at 45° C. The solid was then ground with a pestle andmortar to obtain 2.97 g of a light grey powder. A 1.7 g portion of thissolid was transferred to a porcelain crucible and calcined for 6 hoursat 300° C. to afford 1.0 g of a grey-black powder. The powder XRD (x-raydiffraction) pattern of this sample appears in FIG. 2.

Example 21 Preparation of Aluminum Chlorhydrate (ACH)-Clay Heteroadduct(1.52 mmol Al/g Clay)

With stirring, 30 g of Volclay® HPM-20 clay was added slowly over thecourse of 1 to 2 minutes into a Waring® blender containing 570 g ofdeionized Milli-Q® water while stirring at low speed to afford a greycolloidal dispersion containing no, or substantially no visible lumps orclumps. After the addition was complete, the dispersion was blended athigh speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5wt. % aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 1.66 g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The resulting mixture coagulatedrapidly, and 80 mL of deionized Milli-Q® water was added in order tofacilitate stirring. This mixture was then blended at high speed for 5minutes, and subsequently vacuum filtered through Fisher P8Qualitative-Grade Filter Paper (coarse porosity). After allowing 15 to30 minutes for the filtration, the filtrate pH and conductivity weremeasured (Eutech PCSTestr 35) to provide a pH of 6.2 and a conductivityof 1518 μS/cm. The filtrate was discarded and the remaining wet solidwas re-suspended in 50 to 100 mL of deionized Milli-Q® water.

This filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, filtrate pH/conductivity measurement) wasrepeated until the conductivity of the re-suspended slurry reached 100to 300 μS/cm. In this case, one additional filtration was performed toobtain a slurry with a pH of 6.1 and a conductivity 199 μS/cm. Theremaining wet solid was re-suspended in 150 to 200 mL of 1-butanol androtary evaporated at 45° C. The resulting solid was then ground with apestle and mortar to obtain 3.19 g of a light grey powder. A 1.65 gsample of this solid was transferred to a porcelain crucible andcalcined for 6 hours at 300° C. to afford 0.9 g of a grey-black powder.The powder XRD pattern of this sample appears in FIG. 2.

Example 22 Comparative Example of the Preparation and Single Filtrationof Aluminum Chlorhydrate (ACH)-Clay Heteroadduct (2.5 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 2.71 g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture became viscous quickly,and 100 mL of deionized Milli-Q® water was added in order to facilitatestirring. This mixture was then blended at high speed for 5 minutes,then vacuum filtered through Fisher P8 Qualitative-Grade Filter Paper(coarse porosity). After allowing 15 to 30 minutes for the filtration,the filtrate pH and conductivity were measured (Eutech PCSTestr 35) toprovide a pH of 4.72 and a conductivity of 1988 μS/cm. A portion of thewet solid filter cake was re-suspended in 50 to 100 mL of 1-butanol androtary evaporated at 45° C. The dried solid was then ground with apestle and mortar to obtain 0.66 g of a light grey powder. A 0.64 gportion of this solid was transferred to a porcelain crucible andcalcined for 6 hours at 300° C. to afford 0.5 g of a grey-black powder.

Example 23 Comparative Example of the Preparation and AdditionalWashing/Filtration of Aluminum Chlorhydrate (ACH)-Clay Heteroadduct, asCompared to Example 22 (2.5 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 2.71 g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture became viscous quickly,and 100 mL of deionized Milli-Q® water was added in order to facilitatestirring. The mixture was then blended at high speed for 5 minutes, thenvacuum filtered through Fisher P8 Qualitative-Grade Filter Paper (coarseporosity). After allowing 15 to 30 minutes for the filtration, thefiltrate pH and conductivity were measured (Eutech PCSTestr 35). Thefiltrate was discarded and the remaining wet solid was re-suspended in50 to 100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, filtrate pH/conductivity measurement) wasrepeated until the conductivity of the re-suspended slurry reached 100to 300 μS/cm. In this case, one additional filtration was performed toobtain a slurry with a pH of 4.67 and a conductivity of 87 μS/cm. Theremaining wet solid was re-suspended in 50 to 100 mL of 1-butanol androtary evaporated at 45° C. The dried solid was then ground with apestle and mortar to obtain 3.73 g of a light grey powder. A 1.37 gportion of this solid was transferred to a porcelain crucible andcalcined for 6 hours at 300° C. to afford 0.6 g a grey-black powder. Thepowder XRD pattern of this sample appears in FIG. 2.

Example 24 Comparative Example of the Preparation and Single Filtrationof Aluminum Chlorhydrate (ACH)-Clay Heteroadduct (3.5 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 3.80 g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion, and 20 mL of deionized Milli-Q®water was added in order to facilitate stirring. This mixture was thenblended at high speed for 5 minutes, then vacuum filtered through FisherP8 Qualitative-Grade Filter Paper (coarse porosity). After allowing 15to 30 minutes for the filtration, the filtrate pH and conductivity weremeasured (Eutech PCSTestr 35) to provide a pH of 4.34 and a conductivityof 1500 μS/cm. A portion of the wet solid was re-suspended in 50 to 100mL of 1-butanol and rotary evaporated at 45° C. The dried solid was thenground with a pestle and mortar to obtain 0.74 g of a light grey powder.A 0.62 g portion of this solid was transferred to a porcelain crucibleand calcined for 6 hours at 300° C. to afford 0.5 g a grey-black powder.

Example 25 Comparative Example of the Preparation and AdditionalWashing/Filtration of Aluminum Chlorhydrate (ACH)-Clay Heteroadduct, asCompared to Example 24 (3.5 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 3.80g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. The mixture became viscous quickly,and 20 mL of deionized Milli-Q® water was added in order to facilitatestirring. The mixture was then blended at high speed for 5 minutes, thenvacuum filtered through Fisher P8 Qualitative-Grade Filter Paper (coarseporosity). After allowing 15 to 30 minutes for the filtration, thefiltrate pH and conductivity were measured (Eutech PCSTestr 35). Thefiltrate was discarded and the remaining wet solid was re-suspended in50 to 100 mL of deionized Milli-Q® water.

The filtration process (suspension of the wet solid in deionizedMilli-Q® water, vacuum filtration, filtrate pH/conductivity measurement)was repeated until the conductivity of the re-suspended slurry reached100 to 300 μS/cm. In this case, one additional filtration was performedto obtain a slurry with pH of 4.5, and conductivity of 180 μS/cm. Theremaining slurry was re-suspended in 50 to 100 mL of 1-butanol androtary evaporated at 45° C. The dried solid was then ground with apestle and mortar to obtain 4.33 g of a light grey powder. A 1.36 gportion of this solid was transferred to a porcelain crucible andcalcined for 6 hours at 300° C. to afford 0.6 g a grey-black powder. Thepowder XRD pattern of this sample appears in FIG. 2.

Example 26 Comparative Example of the Preparation of AluminumChlorhydrate (ACH)-Clay Heteroadduct Using Powdered ACH reagent (0.3mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial was charged 0.160g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. Thismixture was poured all at once into the stirred dispersion, and 40 mL ofdeionized Milli-Q® water was added in order to facilitate stirring. Themixture was then blended at high speed for 5 minutes, then vacuumfiltered through Fisherbrand™ P8 Qualitative-Grade Filter Paper (coarseporosity). Filtration was slow (<1 drop/second). After allowing 15 to 30minutes for the filtration, the filtrate pH and conductivity weremeasured (Eutech PCSTestr 35) to provide a pH 6.5 and a conductivity of780 μS/cm. The filtrate was discarded and the remaining wet solid wasre-suspended in 50 mL of deionized Milli-Q® water and centrifuged onceat 3000 rpm to 3500 rpm for 30 to 60 minutes. After removing thesupernatant (having a conductivity of 180 μS/cm), the remaining wetsolid was re-suspended in 50 to 100 mL of 1-butanol and rotaryevaporated. The resulting solid was then ground with a pestle and mortarthen transferred to a porcelain crucible and calcined for 6 hours at300° C. to afford a grey-black powder.

Example 27 Comparative Example of the Preparation of AluminumChlorhydrate (ACH)-Clay Heteroadduct Using Powdered ACH Reagent (0.6mmol Al/g clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial was charged 0.4 gof ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. Thismixture was poured all at once into the stirred dispersion. 40 mL ofdeionized Milli-Q® water was added in order to facilitate stirring. Themixture was then blended at high speed for 5 minutes, then vacuumfiltered through Fisher P8 Qualitative-Grade Filter Paper (coarseporosity). After allowing 15 to 30 minutes for the filtration, thefiltrate pH and conductivity were measured (Eutech PCSTestr 35) toprovide a pH of 7.2 and a conductivity of 180 μS/cm. The filtrate wasdiscarded and the remaining wet solid was re-suspended in 50 mL ofdeionized Milli-Q® water and centrifuged once at 3000 rpm to 3500 rpmfor 30 to 60 minutes. After removing the supernatant (having aconductivity of 180 μS/cm), the remaining wet solid was re-suspended in50 to 100 mL of 1-butanol and rotary evaporated at 45° C. The resultingsolid was then ground with a pestle and mortar to afford 2 g of a greypowder, then transferred to a porcelain crucible and calcined for 6hours at 300° C. to afford a grey-black powder.

Example 28 Preparation and Additional Washing of Aluminum Chlorhydrate(ACH)-Clay Heteroadduct Using Powdered ACH Reagent as Compared toExample 29 (1.52 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial was charged 0.812g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. Thismixture was poured all at once into the stirred dispersion. 20-40 mL ofdeionized Milli-Q® water was added in order to facilitate stirring. Themixture was then blended at high speed for 5 minutes, then vacuumfiltered through Fisher P8 Qualitative-Grade Filter Paper (coarseporosity). After allowing 15 to 30 minutes for the filtration, thefiltrate pH and conductivity were measured (Eutech PCSTestr 35). Theremaining wet solid was re-suspended in 50 to 100 mL of deionizedMilli-Q® water.

The filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, filtrate pH/conductivity measurement) wasrepeated until the conductivity of the supernatant reached 100 to 300μS/cm. In this case, two filtrations were performed to yield a filtratewith pH of 6.3 and a conductivity of 169 μS/cm. The remaining wet solidwas re-suspended in 150 to 200 mL of 1-butanol and rotary evaporated at45° C. The solid was then ground with a pestle and mortar to obtain 3.44g of a light grey powder. A 1.5 g portion of this solid was transferredto a clay crucible and calcined for 6 hours at 300° C. to afford 1.0 gof a grey-black powder.

Example 29 Preparation and Single Filtration of Aluminum Chlorhydrate(ACH)-Clay Heteroadduct Using Powdered ACH Reagent as Compared toExample 28 (1.52 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial was charged 0.812g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. Thismixture was poured all at once into the stirred dispersion.20-40 mL ofdeionized Milli-Q® water was added in order to facilitate stirring. Themixture was then blended at high speed for 5 minutes, then vacuumfiltered through Fisherbrand™ P8 Qualitative-Grade Filter Paper. Afterallowing 15 to 30 minutes for the filtration, the filtrate pH andconductivity were measured (Eutech PCSTestr 35) to provide a pH of 5.8and a conductivity of 1750 μS/cm. A portion of the remaining wet solidwas re-suspended in 50 to 100 mL of 1-butanol and rotary evaporated at45° C. The solid was then ground with a pestle and mortar to afford 1 gof a grey powder, which was then transferred to a porcelain crucible andcalcined for 6 hours at 300° C. to afford 0.6 g of a grey-black powder.

Example 30 Preparation of Aluminum Chlorhydrate (ACH)-Clay HeteroadductUsing Powdered ACH Reagent (1.76 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. To a separate vial was charged 0.940g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. Thismixture was poured all at once into the stirred dispersion. 20 to 40 mLof deionized Milli-Q® water was added in order to facilitate stirring.The mixture was then blended at high speed for 5 minutes, then vacuumfiltered through Fisherbrand™ P8 Qualitative-Grade Filter Paper andwashed with 100 mL of deionized Milli-Q® water. After allowing 15 to 30minutes for the filtration, the filtrate pH and conductivity weremeasured (Eutech PCSTestr 35) to provide a pH of 6.1 and a conductivityof 1799 μS/cm. A portion of the remaining wet solid was re-suspended in50 to 100 mL of 1-butanol and rotary evaporated at 45° C. The solid wasthen ground with a pestle and mortar to afford 1.07 g of a grey powder,which was then transferred to a porcelain crucible and calcined for 6hours at 300° C. to afford 0.9 g of a grey-black powder.

Example 31 Preparation of Aluminum Sesquichlorohydrate-Clay Heteroadduct(1.52 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 1.30 g sample of ALOXICOLL® 31Lsolution was weighed into a vial and added to the dispersion, along withenough deionized Milli-Q® water to facilitate stirring. The mixture wasthen blended at high speed for 5 minutes, and the conductivity wasmeasured (Eutech PCSTestr 35) to provide a conductivity of 2600 μS/cm.The mixture was then vacuum filtered through Fisherbrand™ P8Qualitative-Grade Filter Paper and washed briefly with 100 mL ofdeionized Milli-Q® water. After allowing 15 to 30 minutes for thefiltration, a portion of the remaining wet solid was re-suspended in 50to 100 mL water and the conductivity was once again measured, withtypical conductivities ranging between 100 μS/cm and 500 μS/cm (in thiscase the conductivity was 70 μS/cm). The suspension was then combinedwith 100 to 200 mL of 1-butanol and rotary evaporated at 45° C. Thesolid was then ground with a pestle and mortar to afford 6.2 g of a greypowder, and 1.8 g of this solid was then transferred to a porcelaincrucible and calcined for 6 hours at 300° C. to afford 0.9 g of agrey-black powder.

Example 32 Comparative Example of the Preparation of AluminumSesquichlorohydrate-Clay Heteroadduct (2.5 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 2.79 g sample of ALOXICOLL® 31Lsolution was weighed into a vial and added to the dispersion, along withenough deionized Milli-Q® water to facilitate stirring. The mixture wasthen blended at high speed for 5 minutes, and the conductivity wasmeasured (Eutech PCSTestr 35) to provide a conductivity of 2800 μS/cm.The mixture was then vacuum filtered through Fisherbrand™ P8Qualitative-Grade Filter Paper and washed briefly with 100 mL ofdeionized Milli-Q® water. After allowing 15 to 30 minutes for thefiltration, a portion of the remaining wet solid was re-suspended in 50to 100 mL or water and the conductivity was once again measured (320μS/cm), with typical conductivities ranging between 100 and 500 μS/cm.This suspension was then combined with 100 to 200 mL of 1-butanol androtary evaporated at 45° C. The solid was then ground with a pestle andmortar to afford 5.57 g of a grey powder, and 1.7 g of this solid wasthen transferred to a porcelain crucible and calcined for 6 hours at300° C. to afford 1 g of a grey-black powder.

Example 33 Comparative Example of the Preparation of PolyaluminumChloride (PAC)-Clay Heteroadduct (0.5 mmol Al/g Clay)

A 177.28 gram sample of a 5.0 wt. % Volclay® HPM-20 suspension preparedaccording to the procedure in Example 4 was charged to a Waring®Blender. With stirring, 1.32 g of UltraPAC® 290 solution (GEO) was addedto the HPM-20 clay slurry, after which it was stirred on high for 9minutes. The grey heteroadduct viscous mass was then transferred into aHDPE poly bottle along with 210 grams deionized water in 2 portions. Thegrey heteroadduct slurry was then shaken by hand for approximately 1minute, affording a pH of 4.31 and a conductivity of 1672 μS/cm.Filtration of the slurry through Fisherbrand™ P8 coarse filter paperafforded 28.03 g of wet cake, which was transferred to a HDPE bottle, towhich 308 g of deionized water was also charged. The bottle was shakento afford no lumps in the slurry and a pH of 4.76 and conductivity of200 μS/cm. The slurry was filtered through Fisherbrand™ P8 filter paperto give 22.30 g of wet cake, which was transferred to astir-bar-equipped Erlenmeyer along with 200 mL of n-butanol and stirreduntil no clumps were visible. The stir bar was removed and the mixturerotary evaporated from a 45° C. bath to afford 9.49 g of an off-whitepowder which was lightly ground to a fine powder using a mortar andpestle. 1.10 grams of off-white powder was charged to porcelain crucibleand then a 300° C. oven and calcined for 6 hours to yield 0.8960 gramsof dark grey powder. This powder was cooled to ambient temperature undervacuum before being transferred to an inert atmosphere glove box.

Example 34 Preparation of Polyaluminum Chloride (PAC)-Clay Heteroadduct(1.01 mmol Al/g Clay)

A 201.23 gram sample of a 5.0 wt. % HPM-20 clay suspension prepared asin Example 4 was charged to a Waring® Blender. With stirring, 3.036 g ofUltraPAC® 290 solution (GEO) was added to the HPM-20 slurry. Theresultant thick mass could not be stirred by the Waring® Blender and wastransferred to a HDPE bottle with two triturations of deionized watertotaling 185 g. The bottle was shaken by hand until no clumps or lumpswere visible. The resultant slurry pH was 3.8 and the conductivity was26 mS/cm. The slurry was filtered through Fisherbrand™ Coarse filterpaper no. 8 and the clear filtrate afforded a conductivity of 5.2 mS/cm.A 61 g portion of the filter cake was then transferred to the originalpolymer bottle and re-suspended by shaking in 328 g of deionized wateruntil no lumps were visible. The resultant conductivity was 1116 μS/cmand the pH was 3.93. This slurry was then filtered through Fisherbrand™P8 filter paper. The clear filtrate had a conductivity of 1200 μS/cm. A9.95 g sample of the filter cake was transferred to an Erlenmeyer flask.The remaining filter cake was re-suspended in a new HDPE bottle in 281 gof deionized water, with shaking, to provide a slurry having a pH of4.11 and conductivity of 150 μS/cm. After sitting overnight, the slurrywas filtered through Fisherbrand™ P8 paper and 18.25 g of filter caketransferred to an Erlenmeyer flask along with 100 mL of n-butanol. Theflask was shaken to break up chunks and then rotary evaporated from a40° C. bath, to afford 9.08 g of an off-white powder. A 2.384 g sampleof the off-white powder was charged to a porcelain crucible and placedin a 300° C. oven for 6 hours, affording 1.72 g of grey powder which wasplaced under vacuum to cool down to ambient temperature and then placedin an inert atmosphere glove box.

Example 35 Comparative Example of the Preparation of PolyaluminumChloride (PAC)-Clay Heteroadduct (1.46 mmol Al/g Clay)

A 199.31 g sample of a 5.0 wt. % HPM-20 clay suspension preparedaccording to Example 4 was charged to a Waring® Blender. With stirring,4.36 g of UltraPAC® 290 solution from GEO Specialty Chemicals was addedto the HPM-20 clay slurry. The flask was removed from the blender andswirled until the viscous grey mass could be stirred using the blender,after which it was stirred on high for 9 minutes. The viscous mass wasthen poured into a HDPE polymer bottle along with 2 portions ofdeionized water totaling 85 grams giving a total of 275 g of greyheteroadduct slurry, which was then shaken by hand for approximately 1minute, affording a slurry pH of 3.73 and a conductivity of 6.79 mS/cm.Filtration of the slurry through Fisherbrand™ P8 coarse filter paper,followed by re-suspension of the filter cake in approximately 200 mL ofdeionized water afforded a slurry conductivity of 1 mS/cm. This slurrywas filtered and a 34 g portion of the filter cake was transfer to astir-bar equipped 500 mL Erlenmeyer along with 200 mL of n-butanol. Themixture was stirred overnight to break up the solid chunks. The stir barremoved was then removed and the mixture rotary evaporated from a 45° C.bath to afford 10.78 g of an off-white powder, which was lightly groundto a fine powder using a mortar and pestle. A 1.07 gram portion of theoff-white powder was charged to a porcelain crucible and then calcinedat 300° C. for 6 hours to yield 0.8800 grams of dark grey powder. Thepowder was cooled to ambient temperature under vacuum before beingtransferred to an inert atmosphere glove box.

Example 36 Preparation of Nano-Alumina Clay-Heteroadduct (0.49 gAlumina/g Clay, 4.8 mmol Al/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 80 g sample of 5 wt. % colloidal suspension of HPM-20 clay was addedto a graduated addition funnel. A 9.7 g portion of NYACOL® AL-27dispersion (20% Al₂O₃) was added to a separate addition funnel, and thissuspension was diluted to the 80 mL volume level. The solutions weresimultaneously added into a Waring® blender containing 137 g of Milli-Q®water at low blend speed. The resulting mixture was then blended at highspeed for approximately 5 minutes, and subsequently vacuum filteredthrough Fisher P8 Qualitative-Grade Filter Paper. After allowing 15 to30 minutes for the filtration, the filtrate pH and conductivity weremeasured (Eutech PCSTestr 35) to provide a pH of 9.1 and a conductivityof 451 μS/cm). A portion of the remaining wet solid was re-suspended in50 to 100 mL of 1-butanol and rotary evaporated at 45° C. The resultingsolid was then ground with a pestle and mortar to obtain 1.79 g of alight grey powder, and 0.65 g of this powder was transferred to aporcelain crucible and calcined at 6 hours at 300° C. to afford 0.53 gof a grey powder.

Example 37 Zeta Potential Titration of Fumed Silica with AluminumChlorhydrate

This and subsequent examples demonstrate that “stand-alone” cationicpolymetallates such as ACH can be combined with fumed silica to generatea new cationic colloidal polymetallate system which can function as aheterocoagulation reagent, such that when contacting a colloidal clay, aheterocoagulated clay can form.

A 15 g sample of AEROSIL® 200 fumed silica is combined with 277 g ofdeionized Milli-Q® water in a beaker. The mixture is dispersed using anULTRA-TURRAX® dispersing tool at 5400 rpm for 10 minutes and furtherdispersed at 7000 rpm for an additional 5 minutes to create a 5 wt. %(by silica) dispersion. A 270 g portion of this dispersion istransferred to the measurement vessel of a Colloidal Dynamics ZetaprobeAnalyzer™, containing an axial bottom stirrer. The stirring speed is setfast enough to prevent substantial settling of the dispersion but slowenough to allow the electroacoustic probe to be fully immersed in themixture when fully lowered. Typical stirring speeds are set between 250and 350 rpm, most often 300 rpm.

A 2.5 wt. % solution of aluminum chlorhydrate is prepared by diluting6.16 g of aqueous ACH (50 wt. % aluminum chlorhydrate; GEO SpecialtyChemicals) into 117 g of water. A volumetric zeta potential titration ofthis 2.5 wt. % ACH solution into the aforementioned 5 wt. % AEROSIL® 200dispersion is then performed. Titration settings are 1 mL per titrationpoint, with an equilibration delay of 60 seconds. The resultant data isdepicted in FIG. 7 for ACH-AEROSIL® 200.

The zeta potential versus titrant volume data from FIG. 7 are convertedinto a zeta potential versus AEROSIL® 200 fumed silica mass ratio data,which is plotted in FIG. 8. From FIG. 8, an arbitrary point was selectedat a ratio above 0.04 g ACH/g AEROSIL® 200, corresponding to a zetapotential of approximately +30 mV, and below the ratio of an approximatemonolayer to prepare the heterocoagulation reagent. The ratio ofheterocoagulation reagent to clay was then determined in the usualfashion as set out in Example 8 through Example 11, specifically, byzeta potential titration of the clay with this ACH-fumed silicaheterocoagulation reagent.

Example 38 Zeta Potential Titration of Clay with ACH-Fumed Silica, andDetermination of ACH-SiO₂/Clay Ratio

A 15 g sample of AEROSIL® 200 fumed silica was combined with 277 g ofdeionized Milli-Q® water in a beaker. This mixture was dispersed usingan ULTRA-TURRAX® dispersing tool at 6000 rpm to 7000 rpm for 10 minutes,after which 7.86 g of GEO aluminum chlorohydrate (ACH) solution wasadded. This mixture was then dispersed at 7000 rpm for an additional 5minutes to create a 5 wt. % (by silica) ACH-AEROSIL® 200 fumed silicadispersion.

Separately, 30 g of HPM-20 clay was added slowly over the course of 1 to2 minutes into a Waring® blender containing 570 g of deionized Milli-Q®water while stirring at low speed to afford a grey colloidal dispersioncontaining no, or substantially no visible lumps or clumps. After theaddition was complete, the dispersion was stirred at high speed for 5 to10 minutes to obtain a slightly viscous mixture of 5 wt. % aqueousdispersion of Volclay.

A 60 g sample of this 5 wt. % HPM-20 aqueous dispersion was combinedwith 240 g of deionized Milli-Q® water to give a 1 wt. % HPM-20 aqueousdispersion after shaking. Approximately 280 g of this colloidaldispersion was transferred to the measurement vessel of a ColloidalDynamics Zetaprobe Analyzer™, containing an axial bottom stirrer. Thestirring speed was set as described above. Per the Zetaprobe Analyzer™manual, a zeta potential measurement was performed on this dilutedHPM-20/water dispersion to determine the actual colloidal content of theclay dispersion. Measuring a 5 wt. % HPM-20 aqueous dispersion resultsin a zeta potential of −43 mV. The initial colloidal content estimate isadjusted to match this zeta potential. In this instance, the HPM-20 claycolloidal content of the dispersion was estimated to be 0.86%. TheColloidal Dynamic Zetaprobe Measurement parameters were the following: 5readings, 1 reading/minute; particle density of 2.6 g/cc; dielectricconstant of 4.5.

A volumetric titration of the ACH-AEROSIL® 200 fumed silica dispersioninto the clay dispersion was then performed. Titration settings were 0.2mL per titration point from 0 to 1.2 mL and 0.5 mL per titration pointonwards, with an equilibration delay of 30 seconds, thus providing thedata illustrated in FIG. 9. In this example, the titrant is also acolloidal species. Thus the zeta potential was adjusted using thepreviously described method in Example 11 to provide the plot in FIG. 9.Thus, the amount of AEROSIL® 200 fumed silica in the ACH-AEROSIL® 200fumed silica dispersions used to achieve -20 mV, neutral, and +20 mVzeta potential is summarized in Table 7.

TABLE 7 Results for zeta potential titration of AEROSIL ® 200 and ACHvs. HPM-20 Amount of ACH AEROSIL ® Al molar 200 vs. content vs. AmountVolclay ® Volclay ® of titrant HPM-20 HPM-20 Zeta potential (mL) (g/g)(mmol/g) −20 mV  25 0.45 2.07  0 mV 33 0.59 2.72 +20 mV  40 0.71 3.31

Example 39 Preparation ACH-Fumed Silica/Clay Heteroadduct (3.31 mmolAl/g Clay)

A 15 g sample of AEROSIL® 200 fumed silica was combined with 277 g ofdeionized Milli-Q® water in a beaker, and the mixture was dispersedusing an ULTRA-TURRAX® dispersing tool at 6000-7000 rpm for 10 minutes.A 7.86 g sample of GEO aluminum chlorohydrate solution was then added,followed by dispersion at 7000 rpm for an additional 5 minutes.

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 57 mL sample of the AEROSIL® 200 dispersion was charged to a graduatedaddition funnel, and 80 g of the HPM-20 clay dispersion was transferredto a separate graduated additional funnel. To 135 g of deionizedMilli-Q® water in a Waring® blender, the contents of the additionfunnels were simultaneously added dropwise while stirring. Once additionwas complete the mixture was blended on high speed for 5 to 10 minutes,then vacuum filtered through Fisherbrand™ P8 Qualitative-Grade FilterPaper. After allowing 15 to 30 minutes for the filtration, the filtratepH and conductivity were measured (Eutech PCSTestr 35). The remainingwet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solid in deionized Milli-Q®water, vacuum filtration, filtrate pH/conductivity measurement) wasrepeated until the conductivity of the filtrate reached 100 to 300μS/cm. In this case, two additional filtrations were performed. Theremaining wet solid was re-suspended in 150 to 200 mL of 1-butanol androtary evaporated at 45° C. The solid was then ground with a pestle andmortar to obtain 6.60 g of a light grey powder. A 3.1 g portion of thissolid was transferred to a porcelain crucible and calcined at 6 hours at300° C. to afford 1.45 g of a grey-black powder.

Example 40 Preparation of HCl-Treated Clays (5.28 mmol H+/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

An 80 g sample of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 42.2 mL aliquot of 0.5 M HClaqueous solution was measured into a graduated cylinder and then addedall at once to the clay dispersion. The mixture was then blended at highspeed for 5 minutes and then vacuum filtered through Fisher P8Qualitative-Grade Filter Paper (coarse porosity). After allowing 2 to 3hours for the filtration, the filtrate was discarded and the remainingwet solid was re-suspended in 80 mL of deionized Milli-Q® water. Theresulting suspension's pH and conductivity were measured (EutechPCSTestr 35) to provide a pH of 2.27 and a conductivity of 1560 μS/cm.

This suspension was vacuum filtered again for 2 to 3 hours. Once againthe filtrate was discarded and the remaining wet solid was re-suspendedin 80 mL of deionized Milli-Q® water. The resulting suspension's pH andconductivity were measured (Eutech PCSTestr 35) to provide a pH of 3.09and a conductivity of 217 μS/cm). The remaining wet solid wasre-suspended in 150 to 200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to obtain 0.58 gof light grey flakes. This solid was transferred to a clay crucible andcalcined for 6 hours at 300° C. to afford 0.45 g of a grey powder.

Example 41 Preparation of HCl-Treated Clays (1.5 mmol H⁺/g Clay)

With stirring, 30 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 570 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

An 80 g sample of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 12 mL aliquot of 0.5 M HCl aqueoussolution was measured into a graduated cylinder and then added all atonce to the clay dispersion, and 30 mL of deionized Milli-Q® water wasadded in order to facilitate stirring. This mixture was then blended athigh speed for 5 minutes, then vacuum filtered through Fisher P8Qualitative-Grade Filter Paper (coarse porosity). After allowing 2 to 3hours for the filtration, the filtrate was discarded and the remainingwet solid was re-suspended in 80 mL of deionized Milli-Q® water. Theresulting suspension's pH and conductivity were measured (EutechPCSTestr 35) to provide a pH of 2.56 and a conductivity of 4100 μS/cm.

The suspension was vacuum filtered again for 2 to 3 hours. Once againthe filtrate was discarded and the remaining wet solid was re-suspendedin 80 mL of deionized Milli-Q® water. The resulting suspension's pH andconductivity were measured (Eutech PCSTestr 35) to provide a pH of 3.25and a conductivity of 213 μS/cm. The remaining wet solid wasre-suspended in 150 to 200 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar toobtain 1.73 g of light grey flakes. This solid was transferred to a claycrucible and calcined at 6 hours at 300° C. to afford 1.2 g of a greypowder.

Example 42 Slurry Settling Test for Heterocoagulated Clay (1.52 mmolAl/g Clay)

With stirring, 40 g of HPM-20 clay was added slowly over the course of 1to 2 minutes into a Waring® blender containing 760 g of deionizedMilli-Q® water while stirring at low speed to afford a grey colloidaldispersion containing no, or substantially no visible lumps or clumps.After the addition was complete, the dispersion was blended at highspeed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. Then, 1.66 g of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. An additional 28 mL of deionizedMilli-Q® water was added to the mixture in order to facilitate stirring.The mixture was blended at high speed for 5 minutes, and subsequentlytransferred to a bottle. The blender was washed with an additional 70 gof deionized Milli-Q® water, and 184 g of a slurry was obtained.

The slurry was added to a 250 mL KIMAX® graduated cylinder until itreached the 183 mL mark, and the slurry was left standing undisturbed.Over time, the slurry settled and formed a layer that was substantiallyclear of visible colloidal particles. The volume of this clear layer wasrecorded periodically, and after 95 h (hours) of settling time, thevolume of the clear layer, referred to as the settling volume, was 15mL.

Example 43 Comparative Example of a Slurry Settling Test for anACH-Pillared Clay (5.7 mmol Al/g Clay)

A 5 wt. % aqueous dispersion of HPM-20 clay is prepared by slowly adding40 g of HPM-20 clay over the course of 1 to 2 minutes into a Waring®blender containing 760 g of deionized Milli-Q® water while stirring atlow speed to afford a grey colloidal dispersion containing no, orsubstantially no visible lumps or clumps. After the addition wascomplete, the dispersion was blended at high speed for 5 to 10 minutesto obtain the slightly viscous 5 wt. % aqueous dispersion of HPM-20clay.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. A 6.18 g sample of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. An additional 13.8 mL of deionizedMilli-Q® water was added to the mixture, which was then blended at highspeed for 5 minutes, and subsequently transferred to a bottle. Theblender was washed with an additional 30 g of deionized Milli-Q® water.A 50 g portion of Milli-Q® deionized water was then added to the mixtureto obtain 194 g of a slurry.

The slurry was added to a 250 mL KIMAX® graduated cylinder until itreached the 183 mL mark, and the slurry was left standing undisturbed.Over time, the slurry settled and formed a layer that was substantiallyclear of visible colloidal particles. The volume of this clear layer wasrecorded periodically, and after 95 h (hours) of settling time, thevolume of the clear layer, referred to as the settling volume, was 3 mL.

Example 44 Filtrate Quantification Test for Heterocoagulated Clay (1.52mmol Al/g Clay)

A 5 wt. % aqueous dispersion of HPM-20 clay was prepared as described inExample 42.

A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20 clay wastransferred into a Waring® blender. Then, 1.66 g of GEO aluminumchlorohydrate 50 wt. % aqueous solution was pipetted into a vial and wasadded all at once to the dispersion. An additional 38 mL of deionizedMilli-Q® water was added to the mixture in order to facilitate stirring.The mixture was blended at high speed for 5 minutes, and subsequentlytransferred to a bottle. A total of 110 g of deionized Milli-Q® waterwas then added to the mixture to obtain a slurry with total mass of 250g.

The resulting mixture was then vacuum filtered through an 11 cm FisherP8 Qualitative-Grade Filter Paper inside a 550 mL Buchner funnel, usinga Welch 2034 DryFast™ diaphragm pump. After 10 minutes of filtration,222 g of filtrate was obtained, with 24 g of wet cake remaining. Theresulting filtrate was rotary evaporated at 55° C. to obtain 0.23 g insolid remains.

Example 45 Comparative Example of a Filtrate Quantification Test for anACH-Pillared Clay (5.7 mmol Al/g Clay)

A 5 wt. % aqueous dispersion of HPM-20 clay was prepared as described inExample 43. A 100 g portion of this 5 wt. % aqueous dispersion of HPM-20clay was transferred into a Waring® blender. A 6.18 g sample of GEOaluminum chlorohydrate 50 wt. % aqueous solution was pipetted into avial and was added all at once to the dispersion. An additional 44 g ofdeionized Milli-Q® water was added to the mixture, which was thenblended at high speed for 5 minutes, subsequently transferred to abottle, and 100 g of Milli-Q® deionized water was then added to themixture to obtain a slurry with a total mass of 250 g.

The resulting mixture was then vacuum filtered through an 11 cm FisherP8 Qualitative-Grade Filter Paper inside a 550 mL Buchner funnel, usinga Welch 2034 DryFast™ diaphragm pump. After 20 minutes of filtration, 39g of filtrate was obtained. The unfiltered mixture was allowed to settlefor 96 hours, after which time vacuum filtered using the same filterpaper grade and pump was applied, which yielded an additional 172 g offiltrate with 40 g of wet cake remaining. The resulting filtrate wasrotary evaporated at 55° C. to obtain 1.4 g in solid remains.

Example 46 Preparation of 7-phenyl-2-methyl-indene

Under a nitrogen atmosphere, to a solution of phenylboronic acid (3.05g, 25.0 mmol), Pd₂(dba)₃ (229 mg, 0.25 mmo, dba isdibenzylideneacetone), and K₃PO₄ (15.9 g, 75.0 mmol) in toluene (50 mL)was added P(t-Bu)₃ (202 mg, 1.00 mmol) and 7-bromo-2-methyl-1H-indene(5.23 g, 25.0 mmol). This reaction mixture was stirred vigorously at110° C. for approximately 18 hours, after which time the mixture wascooled to ambient temperature and the solution was passed through silicagel which was washed with dichloromethane. After removal of thevolatiles from the filtrate via rotary evaporation, the resulting crudeproduct of 7-phenyl-2-methyl-1H-indene was purified by columnchromatography (hexane), providing a colorless oil (4.41 g, 86%). An NMRspectrum of the product in CDCl₃, containing a trace of dichloromethaneand water, is shown in FIG. 13.

Example 47 Preparation of the ansa-Metallocene Ligand dimethylsilylenebis(2-methyl-4-phenylindenyl)

Under a N₂ atmosphere, n-BuLi (8.56 mL, 2.5 M in hexane, 21.4 mmol) wasadded to 60 mL of dry toluene, which was then added to a solution of7-phenyl-2-methyl-1H-indene (4.41 g, 21.4 mmol) at room temperature withstirring. After stirring at room temperature for period of 6 h, thereaction mixture was cooled to −35° C. and a solution ofdichlorodimethylsilane (1.29 mL, 10.7 mmol) in THF (5 mL) was added.This mixture was stirred and heated to 80° C. for approximately 18hours. The resulting mixture was cooled to ambient temperature and thesolution was passed through silica gel, washed with dichloromethane, andthe volatiles were removed from the filtrate via rotary evaporation. Theresulting crude product was purified by column chromatography (hexane toEt₂O ratio of 200:1 v:v), providing a yellow solid (2.65 g, 53% yield).

Example 48 Synthesis of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride

A portion of the yellow solid dimethylsilylenebis(2-methyl-4-phenylindenyl) ligand from the prior example (410 mg,0.875 mmol) was dissolved in methyl tert-butyl ether (2 mL) and dilutedwith diethyl ether (2 mL). The solution was cooled to −35° C., and aportion of n-BuLi (0.7 mL, 2.5 M in hexane) was added dropwise withstirring. The resulting red solution was allowed to warm to roomtemperature, stirred overnight, and cooled to −35° C. again. The coldligand solution was then added to a slurry of ZrCl₄(THF)₂ (333 mg, 0.875mmol) in hexane (10 mL), which was cooled to −35° C. in advance. Theresulting orange slurry was allowed to warm to room temperature andstirred overnight, after which the volatile components were removedunder vacuum, and the residual solid was extracted with dichloromethane(DCM). After passing the dichloromethane extract through a syringefilter, the solution was concentrated until orange crystals formed.Hexane was added to allow more product to precipitate. The crystallinesolid was collected by filtration and dried under high vacuum (280 mg,51% yield). The product was recrystallized in dichloromethane(DCM)/hexane (1/1, v:v) to afford 145 mg of crystals, which wererecrystallized from DCM one additional time to give 60 mg of essentiallyisomerically pure, rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride. The ¹H NMR spectrumof the re-crystallized product in CDCl₃, containing a trace amount ofdichloromethane, is shown in FIG. 14.

Example 49 Propylene Polymerization Catalyzed by rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, Calcined ClayHeteroadduct of Example 17, and Trialkylaluminum

To a solution of 6.0 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)-zirconium dichloride from Example 45 in 2mL of toluene was added 1.3 mL of tri-n-octyl aluminum (TnOA, 1.2 mmol).The resulting solution was mixed with 75 mg of the single filtration,azeotroped, and calcined aluminum chlorhydrate clay heteroadduct (1.76mmol Al/g clay) according to Example 17. The resulting slurry was shakenfor 2 minutes and maintained at room temperature for several hoursbefore use.

Propylene polymerization was conducted in a bench scale 2-liter reactorper the following procedure. The reactor was first preheated to at least100° C. with a nitrogen purge to remove residual moisture and oxygen,and was thereafter cooled to 50° C. Under nitrogen, 1 liter (L) of dryheptane was introduced into the reactor. When reactor temperature wasabout 50° C., 2.0 mL of tri-n-octylaluminum (0.92 M, in hexanes), andthen catalyst slurry prepared as above were added to the reactor. Thepressure of the reactor was raised to 28.5 psig at 50° C. by introducingnitrogen.

The reactor temperature was then raised to 70° C., and the total reactorpressure was raised to and controlled at 90 psig by continuallyintroducing propylene into the reactor and the polymerization wasallowed to proceed for 1 hour. After this time, the reactor was ventedto reduce the pressure to 0 psig and the reactor temperature was cooledto 50° C. The reactor was opened, and 500 mL of methanol was added tothe reactor contents, and the resulting mixture was stirred for 5minutes and then filtered to obtain the polymer product. The obtainedpolymer was vacuum dried at 80° C. for 6 hours. The polymer wasevaluated for melt flow rate (MFR) and isotacticity, and the activity ofcatalyst was also determined. Table 8 below summarizes the propylenepolymerization results of this example.

TABLE 8 Propylene polymerization runs according Examples 46 and 47,catalyzed by rac-dimethylsilylene bis(2-methyl-4-phenylindenyl)zirconiumdichloride, calcined clay heteroadduct, and trialkylaluminum Poly-Calcined Clay propylene Heteroadduct Polymerization (PP) Yield Activity(amount, mg) T (° C.) Example (g) (g_(PP) g_(cat) ⁻¹ h⁻¹) Example 17 70°C. Example 49 11.7 156 (75 mg) Example 16 80° C. Example 50 21.6 288 (75mg)

Example 50 Propylene Polymerization Catalyzed by rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, Calcined ClayHeteroadduct of Example 16, and Trialkylaluminum

The procedure in Example 49 was repeated using the spray dried andcalcined washed clay heteroadduct of Example 16, and carrying out thepolymerization at a temperature 80° C. rather than 70° C. as in Example49. Table 8 summarizes the propylene polymerization results of thisexample.

Example 51 Ethylene Homopolymerization Catalysis Inventive andComparative Supports and Metallocene Catalysts

Homopolymerization of ethylene was conducted at 450 total psi and 90° C.using the reaction procedure and conditions described previously. Theresults are provided in Table 3A.

Although the invention herein has been described with reference toparticular aspects or embodiments, it is to be understood that theseaspects and embodiments are merely illustrative of the principles andapplications of the present invention. These and other descriptionsaccording to the disclosure can further include the various embodimentsand aspects presented below.

ADDITIONAL EXAMPLES

Table 9 illustrates some actual and constructive examples of componentsthat can be selected and used to prepare the heterocoagulated clayactivator support, and additional components that can be selected andused in combination with the activator support to generate the olefinpolymerization catalyst. Any one or more than one of the compounds orcompositions set out in each component listing can be selectedindependently of any other compound or composition set our in any othercomponent listing. For example, this table discloses that any one ormore than one of Component 1, any one or more than one of Component 2,optionally any one or more than one of Component A, and optionally anyone or more than one of Component B, can be selected independently ofeach other and combined or contacted in any order to provide theheterocoagulated clay activator support, as disclosed herein. Any one ormore than one of Component 3 (metallocene), optionally any one or morethan one of Component C, and optionally any one or more than one ofComponent D, can be selected independently of each other and combined orcontacted in any order with each other and the heterocoagulated clayactivator support to provide an olefin polymerization catalyst, asdisclosed herein.

TABLE 9 Actual and constructive examples of components that can beselected independently and used to prepare a heterocoagulated clayactivator support and an olefin polymerization catalyst. Component 2Component 1 Heterocoagulation reagent Optional Component A OptionalComponent B Colloidal smectite clay (cationic polymetallate) Metal oxideSurfactant Montmorillonite Aluminum chlorohydrate Fumed silica Anionicsurfactants Sauconite Aluminum Fumed alumina (sulfates, phosphates)Nontronite sesquichlorohydrate Fumed silica-alumina Cationic surfactants(alkyl Hectorite Polyaluminum chloride Metal oxide sols (silica,ammonium compounds) Beidellite Combinations thereof alumina,silica-alumina) Nonionic surfactants Saponite Combinations thereof(polyglycol ethers, Bentonite ethoxylates) Combinations thereofCombinations thereof Component 1 + Component 2 + Optionally, ComponentA + Optionally, Component B

Heterocoagulated Activator Support Heterocoagulated Component 3 OptionalComponent C Optional Component D Activator Support MetalloceneCo-Catalyst Co-Activator From above

 

 

 

Alkylaluminum compounds (TEA, TnOA, TiBA) Organozinc/ organomagnesiumcompounds Organolithium compounds Alkylboron compounds Hydriding agents(LiAlH₄, NaBH₄) Combinations thereof Aluminoxanes (MAO, EAO)Alkylammonium tetrafluoroborates Solid oxides Organoborons (alkylborons,fluoroborate salts) Fluorided/chloride/sulfated aluminasFluorided/sulfated/chlorided silica-aluminas Combinations thereof (andrac isomers) R = H, hydrocarbyl group, Si- containing hydrocarbyl; Y =carbon or silicon; M = group 4 metal; Q = halogen, hydrocarbyl, Si-containing hydrocarbyl with no β-hydrogens; J = integer from 1 to 4,inclusive Combinations thereof Heterocoagulated Activator Support +Component 3 + Optionally, Component C + Optionally, Component D

Olefin Polymerization Catalyst

In Table 9, certain abbreviations are used which will be understood bythe person of ordinary skill, such as TEA (triethylaluminum), TnOA(tri-n-octylaluminum), TiBA (triisobutylaluminum), MAO(methylaluminoxane), EAO (ethylaluminoxane), and the like. Unlessotherwise specified, groups such as “hydrocarbyl” or “Si-containinghydrocarbyl” groups may be considered to have from 1 to about 12carbons, such as for example, methyl, n-propyl, phenyl,trimethylsilylmethyl, neopentyl, and the like. In Table 9, each group orsubstituent is selected independently of any other group of substituent.Therefore, each “R” substituent is selected independently of any other Rsubstituent, each “Q” group is selected independently of any other Qgroup, and the like.

Also with respect to Table 9, the co-catalyst component is referred toas optional (Optional Component C), and includes alkylating agents,hydriding agents and the like. A co-catalyst component such as thoselisted is typically used in the formation of the polymerization catalystbecause the metallocene is commonly halide-substituted and theco-catalyst can provide a polymerization-activatable/initiating ligandsuch as methyl or hydride.

Aspects of the Disclosure

Aspect 1. A catalyst composition for olefin polymerization, the catalystcomposition comprising:

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined smectiteheteroadduct, the smectite heteroadduct comprising the contact productof [1] a colloidal smectite clay and [2] a heterocoagulation reagentcomprising at least one cationic polymetallate in a liquid carrier andin an amount sufficient to provide a slurry of the smectite heteroadducthaving a zeta potential in a range of from about positive 25 mV(millivolts) to about negative 25 mV.

Aspect 2. A process for polymerizing olefins comprising contacting atleast one olefin monomer and a catalyst composition under polymerizationconditions to form a polyolefin, wherein the catalyst compositioncomprises:

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined smectiteheteroadduct, the smectite heteroadduct comprising the contact productof [1] a colloidal smectite clay and [2] a heterocoagulation reagentcomprising at least one cationic polymetallate in a liquid carrier andin an amount sufficient to provide a slurry of the smectite heteroadducthaving a zeta potential in a range of from about positive 25 mV(millivolts) to about negative 25 mV.

Aspect 3. A method of making an olefin polymerization catalyst, themethod comprising contacting in any order:

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined smectiteheteroadduct, the smectite heteroadduct comprising the contact productof [1] a colloidal smectite clay and [2] a heterocoagulation reagentcomprising at least one cationic polymetallate in a liquid carrier andin an amount sufficient to provide a slurry of the smectite heteroadducthaving a zeta potential in a range of from about positive 25 mV(millivolts) to about negative 25 mV.

Aspect 4. A support-activator comprising an isolated smectiteheteroadduct, the smectite heteroadduct comprising the contact productin a liquid carrier of [1] a colloidal smectite clay and [2] aheterocoagulation reagent comprising at least one cationic polymetallateand in an amount sufficient to provide a slurry of the smectiteheteroadduct having a zeta potential in a range of from about positive25 mV (millivolts) to about negative 25 mV.

Aspect 5. A method of making a support-activator, the method comprising:

a) providing a colloidal smectite clay;

b) contacting in a liquid carrier the colloidal smectite clay with aheterocoagulation reagent comprising at least one cationic polymetallateand in an amount sufficient to provide a slurry of a smectiteheteroadduct having a zeta potential in a range of from about positive25 mV (millivolts) to about negative 25 mV; and

c) isolating the smectite heteroadduct from the slurry.

Aspect 6. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-5, wherein the liquid carrier comprises, consists of, consistsessentially of, or is selected from:

water; an alcohol such as methanol, ethanol, n-propanol, isopropanol, orn-butanol; an ether such as diethyl ether or di-n-butyl ether; a ketonesuch as acetone; an ester such as methyl acetate or ethyl acetate; orany combination thereof; and

optionally further includes a surfactant which comprises, consists of,consists essentially of, or is selected from:

-   -   an anionic surfactant such as a sulfate, a sulfonate, a        phosphate, carboxylate, or other anionic surfactants, examples        of which include but are not limited to dialkyl sulfocarboxylic        acid esters, alkyl aryl sulfonic acid salts, alkyl sulfonic acid        salts, sulfosuccinic acid esters, fatty acid alkali salts,        polycarboxylic acid salts, polyoxyethylene alkyl ether        phosphoric acid ester salts, alkylnaphthalene sulfonic acid        salts, wherein the salts can be selected form salts of an alkali        metal such as lithium, sodium or potassium, an alkaline earth        metal such as calcium or magnesium, or ammonium or        hydrocarbylammonium;    -   a cationic surfactant such as a primary, secondary, or tertiary        amine or ammonium compound or a quaternary ammonium compound,        and the like, examples of which include but are not limited to        tetrabutylammonium bromide, dioctadecyldimethylammonium        chloride, hexadecyltrimethylammonium chloride, octadecylammonium        chloride, trimethylstearylammonium chloride, or        cetyltrimethylammonium bromide;    -   a non-ionic surfactant such as ethoxylates, glycol ethers, fatty        alcohol polyglycol ethers, combinations thereof, or other        non-ionic surfactants, examples of which include but are not        limited to octylphenol ethoxylate, polyethylene glycol        tert-octylphenyl ether, ethylenediamine        tetrakis(ethoxylate-block-propoxylate) tetrol, or        ethylenediamine tetrakis(propoxylate-block-ethoxylate) tetrol;        or    -   an amphoteric surfactant comprising an anionic surfactant moiety        and a cationic surfactant in the same molecule.

Aspect 7. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-5, wherein the isolated smectiteheteroadduct is [1] washed with water, [2] heated, dried, and/orcalcined, or [3] washed with water and heated, dried, and/or calcined.

Aspect 8. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-5, wherein the smectite heteroadductis:

a) isolated from the slurry by filtration or by an azeotroping process;and/or

b) isolated from the slurry without the use of ultrafiltration,centrifugation, or settling tanks.

Aspect 9. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-5, wherein the smectite heteroadductis isolated from the slurry by ultrafiltration, centrifugation, orsettling tanks.

Aspect 10. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-5 or 7-9, wherein the isolatedsmectite heteroadduct is further dried or calcined by heating in air, inan inert atmosphere, or under vacuum.

Aspect 11. A support-activator or a method of making a support-activatoraccording to Aspect 10, wherein the heating is carried out to atemperature of at least about 100° C.

Aspect 12. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-11, wherein the smectite clay is [1] natural or synthetic,and/or [2] a dioctahedral smectite clay.

Aspect 13. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-12, wherein:

a) the smectite clay is colloidal; and/or

b) the smectite clay has an average particle size of less than about 10μm (microns), less than about 5 μm, less than about 3 μm, less than 2μm, or less than 1 μm, wherein the average particle size is greater thanabout 15 nm, greater than about 25 nm, greater than about 50 nm, orgreater than about 75 nm.

Aspect 14. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-13, wherein the smectite clay comprises, consists of, consistsessentially of, or is selected from montmorillonite, sauconite,nontronite, hectorite, beidellite, saponite, bentonite, or anycombination thereof.

Aspect 15. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one of theprevious aspects such as Aspects 1-13, wherein the smectite claycomprises structural units characterized by the following formula:

(M^(A)IV)₈(M^(B)VI)_(p)O₂₀(OH)₄; wherein

a) M^(A)IV is a four-coordinate Si⁴⁺, wherein the Si⁴⁺ is optionallypartially substituted by a four-coordinate cation that is not Si⁴⁺;

b) M^(B)VI is a six-coordinate Al³⁺ or Mg²⁺, wherein the Al³⁺ or Mg²⁺ isoptionally partially substituted by a six-coordinate cation that is notAl³⁺ or Mg²⁺;

c) p is four for cations with a +3 formal charge, or p is 6 for cationswith a +2 formal charge; and

d) any charge deficiency that is created by the partial substitution ofa cation that is not Si⁴⁺ at M^(A)IV and/or any charge deficiency thatis created by the partial substitution of a cation that is not Al³⁺ orMg²⁺ at M^(B)VI is balanced by cations intercalated between structuralunits.

Aspect 16. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 15,wherein:

a) in each occurrence, the cation that is not Si⁴⁺ is independentlyselected from Al³⁺, Fe³⁺, P⁵⁺, B³⁺, Ge⁴⁺, Be²⁺, Sn⁴⁺, and the like;

b) in each occurrence, the cation that is not Al³⁺ or Mg²⁺ isindependently selected from Fe³⁺, Fe²⁺, Ni²⁺, Co²⁺, Li⁺, Zn²⁺, Mn²⁺,Ca²⁺, Be²⁺, and the like; and/or

c) the cations intercalated between structural units are selected frommonocations, dications, trications, other multications, or anycombination thereof.

Aspect 17. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 15,wherein:

a) in each occurrence, the cation that is not Si⁴⁺ is independentlyselected from Al³⁺ or Fe³⁺; and

b) in each occurrence, the cation that is not Al³⁺ or Mg²⁺ isindependently selected from Fe³⁺, Fe²⁺, Ni²⁺, or Co²⁺.

c) the cations intercalated between structural units are selected frommonocations.

Aspect 18. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-17, wherein the smectite clay is monocation exchanged with atleast one of lithium, sodium, or potassium.

Aspect 19. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from a cationic oligomeric orcationic polymeric aluminum species.

Aspect 20. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from polyaluminum chloride,aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminumoxyhydroxychloride.

Aspect 21. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 20,wherein the ratio of millimoles (mmol) of aluminum (Al) in thepolyaluminum chloride, aluminum chlorhydrate, aluminumsesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) ofcolloidal smectite clay is in a range of from about 0.2 mmol Al/g clayto about 2.5 mmol Al/g clay, from about 0.5 mmol Al/g clay to about 2.2mmol Al/g clay, from about 0.75 mmol Al/g clay to about 2.0 mmol Al/gclay, or from about 1.0 mmol Al/g clay to about 1.8 mmol Al/g clay.

Aspect 22. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 20,wherein the ratio of millimoles (mmol) of aluminum (Al) in thepolyaluminum chloride, aluminum chlorhydrate, aluminumsesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) ofcolloidal smectite clay isolated or calcined smectite heteroadduct isabout 70% or less, about 60% or less, about 50% or less, about 45% orless, about 40% or less, or about 35% or less of a comparative ratio ofmillimoles of aluminum to grams of colloidal clay used for thepreparation of a pillared clay using the same colloidal smectite clayand heterocoagulation reagent.

Aspect 23. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises linear,cyclic or cluster aluminum compounds containing from 2-30 aluminumatoms.

Aspect 24. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-19, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from a first metal oxide whichis chemically-treated with a second metal oxide, a metal halide, a metaloxyhalide, or a combination thereof in an amount sufficient to provide acolloidal suspension of the chemically-treated first metal oxide havinga zeta potential of greater than positive 20 mV (millivolts).

Aspect 25. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 24,wherein the first metal oxide comprises, consists of, consistsessentially of, or is selected from fumed silica, fumed alumina, fumedsilica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumedzirconia, fumed ceria, or any combination thereof.

Aspect 26. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 24,wherein:

the first metal oxide comprises SiO₂ or Al₂O₃, and wherein the secondmetal oxide, the metal halide, or the metal oxyhalide is obtained froman aqueous solution or suspension of a metal oxide, hydroxide,oxyhalide, or halide, such as ZrOCl₂, ZnO, NbOCl₃, B(OH)₃, AlCl₃, or acombination thereof; or

the first metal oxide comprises SiO₂, and wherein the second metaloxide, the metal halide, or the metal oxyhalide comprises Al₂O₃, ZnO,AlCl₃, or a combination thereof.

Aspect 27. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate composition comprises,consists of, consists essentially of, or is selected from:

fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumedzinc oxide, fumed titania, fumed zirconia, fumed ceria, or anycombination thereof; which is

chemically-treated with polyaluminum chloride, aluminum chlorhydrate,aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or anycombination thereof.

Aspect 28. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein:

a) the colloidal smectite clay comprises colloidal montmorillonite, suchas HPM-20 Volclay; and

b) the heterocoagulation reagent comprises aluminum chlorhydrate,polyaluminum chloride, or aluminum sesquichlorohydrate.

Aspect 29. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from boehmite, fumedsilica-alumina, colloidal ceria, colloidal zirconia, magnetite,ferrihydrite, any positively charged colloidal metal oxide, or anycombination thereof.

Aspect 30 A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from aluminumchlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumedalumina, aluminum chlorhydrate-treated fumed silica-alumina, or anycombination thereof.

Aspect 31. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from an aluminum species or anycombinations of species having the empirical formula:

Al₂(OH)_(n)Cl_(m)(H₂O)_(x),

wherein n+m=6, and x is a number from 0 to about 4.

Aspect 32. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from aluminum species having theempirical formula 0.5[Al₂(OH)₅Cl(H₂O)₂] or [AlO₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺(“Al₁₃-mer”) polycation.

Aspect 33. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from an oligomer prepared bycopolymerizing soluble rare earth salts with a cationic metal complex ofat least one additional metal selected from aluminum, zirconium,chromium, iron, or a combination thereof, according to U.S. Pat. No.5,059,568.

Aspect 34. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 33,wherein the at least one rare earth metal is selected from cerium,lanthanum, or a combination thereof.

Aspect 35. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from a complex of Formula I orFormula II or any combination of complexes of Formula I or Formula II,according to the following formulas:

[M(II)_(1-x)M(III)_(x)(OH)₂]A_(x/a).m L   (I)

[LiAl₂(OH)₆]A_(l/n).m L   (II)

wherein:

M(II) is at least one divalent metal ion;

M(III) is at least one trivalent metal ion;

A is at least one inorganic anion;

L is an organic solvent or water;

n is the valence of the inorganic anion A or, in the case of a pluralityof anions A, is their mean valence; and

x is a number from 0.1 to 1; and

m is a number from 0 to 10.

Aspect 36. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 35,wherein:

M(II) comprises, consists of, consists essentially of, or is selectedfrom zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium,manganese, copper, or magnesium;

M(III) comprises, consists of, consists essentially of, or is selectedfrom iron, chromium, manganese, bismuth, cerium, or aluminum;

A comprises, consists of, consists essentially of, or is selected fromhydrogencarbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate,chloride, bromide, fluoride, hydroxide, or carbonate.

n is a number from 1 to 3; and

L comprises, consists of, consists essentially of, or is selected frommethanol, ethanol or isopropanol, or water.

Aspect 37. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 35,wherein the cationic polymetallate is selected from a complex of FormulaI, wherein M(II) is magnesium, M(III) is aluminum, and A is carbonate.

Aspect 38. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from a layered double hydroxideor a mixed metal layered hydroxide.

Aspect 39. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 38,wherein the mixed metal layered hydroxide is selected from a Ni—Al,Mg—Al, or Zn—Cr—Al type having a positive layer charge.

Aspect 40. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 39,wherein the layered double hydroxide or mixed metal layered hydroxidecomprises, consists of, consists essentially of, or is selected frommagnesium aluminum hydroxide nitrate, magnesium aluminum hydroxidesulfate, magnesium aluminum hydroxide chloride,Mg_(x)(Mg,Fe)₃(Si,Al)₄O₁₀(OH)₂(H₂O)₄ (x is a number from 0 to 1, forexample, about 0.33 for ferrosaponite), (Al,Mg)₂Si₄O₁₀(OH)₂(H₂O)₈,synthetic hematite, hydrozincite (basic zinc carbonate) Zn₅(OH)₆(CO₃)₂,hydrotalcite [Mg₆Al₂(OH)₁₆]CO₃.4H₂O, tacovite [Ni₆Al₂(OH)₆]CO₃.4H₂O,hydrocalumite [Ca₂Al(OH)₆]OH.6H₂O, magaldrate[Mg₁₀Al₅(OH)₃₁](SO₄)₂.mH₂O, pyroaurite [Mg₆Fe₂(OH)₁₆]CO₃.4.5H₂O,ettringite [Ca₆Al₂(OH)₁₂](SO₄)₃.26H₂O, or any combination thereof.

Aspect 41. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-18, wherein the cationic polymetallate comprises, consists of,consists essentially of, or is selected from an iron polycation havingan empirical formula FeO_(x)(OH)_(y)(H₂O)_(z)]^(n+), wherein 2x+y isless than (<) 3, z is a number from 0 to about 4, and n is a number from1 to 3.

Aspect 42. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-41, wherein the slurry of the smectite heteroadduct ischaracterized by a conductivity in a range of from about 20,000 μS/cm toabout 100 μS/cm, from about 10,000 μS/cm to about 200 μS/cm, or fromabout 1000 μS/cm to about 300 μS/cm, when the concentration of theslurry is greater than or equal to about 1 wt. % or greater than orequal to about 2.5 wt. % solids, or when the concentration of the slurryis in a range of from about 1 wt. % to about 10 wt. % solids, from about2.5 wt. % to about 10 wt. % solids, or from about 5 wt. % to about 10wt. % solids.

Aspect 43. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-41, wherein the slurry of the smectite heteroadduct ischaracterized by a conductivity of less than 10 mS/cm, less than 5mS/cm, or less than 1 mS/cm, or wherein the slurry of the smectiteheteroadduct is characterized by a conductivity in a range of from 2mS/cm to 10 μS/cm, from 1 mS/cm to 50 μS/cm, or from 500 μS/cm to 100μS/cm, when the concentration of the slurry is greater than or equal toabout 1 wt. % or greater than or equal to about 2.5 wt. % solids, orwhen the concentration of the slurry is in a range of from about 1 wt. %to about 10 wt. % solids, from about 2.5 wt. % to about 10 wt. % solids,or from about 5 wt. % to about 10 wt. % solids.

Aspect 44. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the smectite heteroadduct is calcined using anyone of the following conditions:

a) a temperature ranging from about 110° C. to about 600° C. and for atime period ranging from about 1 hour to about 10 hours;

b) a temperature ranging from about 150° C. to about 500° C. and for atime period ranging from about 1.5 hours to about 8 hours; or

c) a temperature ranging from about 200° C. to about 450° C. and for atime period ranging from about 2 hours to about 7 hours.

Aspect 45. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the smectite heteroadduct is calcined in air at atemperature in a range of from 200° C. to 750° C., from 225° C. to 700°C., from 250° C. to 650° C., from 225° C. to 600° C., from 250° C. to500° C., from 225° C. to 450° C., or from 200° C. to 400° C.

Aspect 46. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-45, wherein the smectite heteroadduct is calcined in anatmosphere comprising air or carbon monoxide or in an inert atmospheresuch as nitrogen.

Aspect 47. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-45, wherein the smectite heteroadduct is calcined in air orcarbon monoxide in a fluidized bed.

Aspect 48. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the smectite heteroadduct is calcined in anatmosphere of air or an atmosphere that comprises carbon monoxide in afluidized bed at a temperature in a range of from 100° C. to 900° C.,from 200° C. to 800° C., from 250° C. to 600° C., or from 300° C. to500° C.

Aspect 49. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the calcined smectite heteroadduct is calcined ata temperature of 250° C. or higher.

Aspect 50. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the calcined smectite heteroadduct is calcined ata temperature of 300° C. or higher.

Aspect 51. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-43, wherein the calcined smectite heteroadduct is calcined ata temperature of 350° C. or higher.

Aspect 52. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-51, wherein the calcined smectite heteroadduct is absent orsubstantially absent ordered domains characterized by a powder X-raydiffraction (XRD) peak in a range of from 0 degrees 2θ (2 theta) to 13degrees 2θ.

Aspect 53. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-51, wherein the calcined smectite heteroadduct ischaracterized by any of the following features:

a) the presence or the substantial absence of a uniform intercalatedstructure having a d001 basal spacing of greater than or equal to about13 Å (Angstrom) in the powder X-Ray Diffraction (XRD);

b) the presence or the substantial absence of a uniform intercalatedstructure having a d001 basal spacing in a range of from about 9 Å(Angstrom) to about 13 Å (Angstrom) in the powder X-Ray Diffraction(XRD), or alternatively, in a range of from about 10 Å (Angstrom) toabout 13 Å (Angstrom), in the powder X-Ray Diffraction (XRD); or

c) the combination of a) and b).

Aspect 54. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-51, wherein the sample of calcined smectite heteroadduct ischaracterized by a non-smectite heteroadduct intercalated structurecharacterized by a powder X-ray diffraction (XRD) peak in a range offrom about 4 degrees 2θ (2 theta) to about 5 degrees 2θ, wherein thenon-smectite heteroadduct intercalated structure is present at aconcentration of less than 60 wt. %, less than 50 wt. %, less than 40wt. %, less than 30 wt. %, less than 20 wt. %, less than 10 wt. %, orless than 5 wt. % in the sample of calcined smectite heteroadduct.

Aspect 55. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-54, wherein the calcined smectite heteroadduct exhibits a BJHporosity in a range of from about 0.2 cc/g to about 3.0 cc/g, from about0.3 cc/g to about 2.5 cc/g, or from about 0.5 cc/g to about 1.8 cc/g.

Aspect 56. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-55, wherein the calcined smectite heteroadduct exhibits acombined cumulative pore volume of pores between 3-10 nm diameter(V_(3-10 nm)) which is less than 55%, less than 50%, less than 45%, orless than 40% of the combined cumulative pore volume of pores between3-30 nm (V_(3-30 nm)).

Aspect 57. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-56, wherein the calcined smectite heteroadduct exhibits alogarithmic differential pore volume distribution (dV (log D) vs. porediameter) having a local maximum in a range of from 30 Å (Angstroms) to40 Å (D_(VM(30-40))).

Aspect 58. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-57, wherein the calcined smectite heteroadduct ischaracterized by a logarithmic differential pore volume distribution (dV(log D) vs. pore diameter) having a highest value (D_(M), representingthe most frequently appearing pore diameter) in a range of from 30 Å(Angstroms) to 40 Å (D_(VM(30-40))) or in a range of from 200 Å(Angstroms) to 500 Å (D_(VM(200-500))).

Aspect 59. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 58,wherein the local maximum D_(VM(30-40)) is a global maximum.

Aspect 60. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 58,wherein the local maximum D_(VM(30-40)) is less than 210%, less than150%, less than 120%, or less than 100% of a local maximum between 200 Å(Angstroms) and 500 Å (D_(VM(200-500))).

Aspect 61. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to Aspect 58,wherein the logarithmic differential pore volume distribution (dV (logD) vs. pore diameter) exhibits a local maximum between 200 Å (Angstroms)and 500 Å (D_(VM(200-500))) which exceeds all values of dV (log D)between 30 Å (Angstroms) and 200 Å.

Aspect 62. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-61, wherein the heterocoagulation reagent comprises analuminum concentration in a range of:

a) from about 1 wt. % to about 60 wt. % calculated on the basis ofAl₂O₃;

b) from about 5 wt. % to about 50 wt. % calculated on the basis ofAl₂O₃;

b) from about 10 wt. % to about 45 wt. % calculated on the basis ofAl₂O₃; or

c) from about 15 wt. % to about 35 wt. % calculated on the basis ofAl₂O₃.

Aspect 63. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-62, wherein [1] the colloidal smectite clay and the [2]heterocoagulation reagent are contacted in an amount sufficient toprovide a slurry of the smectite heteroadduct having a zeta potential ina range of:

a) from about positive (+)22 mV (millivolts) to about negative (−)22 mV;

b) from about positive (+)20 mV (millivolts) to about negative (−)20 mV;

c) from about positive (+)18 mV (millivolts) to about negative (−)18 mV;

d) from about positive (+)15 mV (millivolts) to about negative (−)15 mV;

e) from about positive (+)12 mV (millivolts) to about negative (−)12 mV;

f) from about positive (+)10 mV (millivolts) to about negative (−)10 mV;

g) from about positive (+)8 mV (millivolts) to about negative (−)8 mV;or

h) from about positive (+)5 mV (millivolts) to about negative (−)5 mV.

Aspect 64. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-63, wherein [1] the colloidal smectite clay and the [2]heterocoagulation reagent are contacted at 25° C.±5° C. for a timeperiod of less than 1 hour, less than 45 minutes, less than 30 minutes,less than 20 minutes, less than 15 minutes, or less than 10 minutes.

Aspect 65. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-64, wherein following contacting [1] the colloidal smectiteclay and the [2] heterocoagulation reagent, the smectite heteroadduct isisolated from the slurry by filtration without the use ofultrafiltration, centrifugation, or settling tanks.

Aspect 66. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-65, wherein the smectite heteroadduct is amorphous.

Aspect 67. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-66, wherein the catalyst composition or the support-activatorfurther comprises an ion-exchanged clay, a protic-acid-treated clay, apillared clay, an aluminoxane, a borate co-activator, or any combinationthereof.

Aspect 68. A catalyst composition, a process for polymerizing olefins, amethod of making an olefin polymerization catalyst, a support-activator,or a method of making a support-activator according to any one ofAspects 1-66, wherein the catalyst composition or the support-activatoris substantially absent an ion-exchanged clay, a protic-acid-treatedclay, a pillared clay, an aluminoxane, a borate co-activator, or anycombination thereof.

Aspect 69. A method of making a support-activator according to any oneof Aspects 5-68, wherein the smectite heteroadduct is subsequently driedand/or calcined.

Aspect 70. A method of making a support-activator according to any oneof Aspects 5-69, wherein the smectite heteroadduct is subsequently driedby heating, azeotropic drying, freeze drying, flash drying, fluidizedbed drying, spray drying, or any combination thereof.

Aspect 71. A method of making a support-activator according to any oneof Aspects 5-70, wherein after isolating the smectite heteroadduct, thesmectite heteroadduct is wet milled or dry milled.

Aspect 72. A method of making a support-activator according to any oneof Aspects 5-71, wherein the isolated smectite heteroadduct is dried toa constant weight to obtain a dry smectite heteroadduct.

Aspect 73. A method of making a support-activator according to any oneof Aspects 5-71, wherein the smectite heteroadduct is calcined at atemperature in a range of from about 110° C. to about 900° C., for atime period in a range of from about 1 hour to about 12 hours.

Aspect 74. A method of making a support-activator according to any oneof Aspects 5-71, wherein the smectite heteroadduct is calcined for atime and temperature sufficient to achieve a catalyst productivity of atleast about 1,500 g polymer/g support-activator, or a catalystproductivity in a range of from about 1,500 g polymer/gsupport-activator to about 30,000 g polymer/g support-activator.

Aspect 75. A method of making a support-activator according to any oneof Aspects 5-71, further comprising the step removing entrapped air fromthe dried or calcined smectite heteroadduct by [1] exposing the dried orcalcined smectite heteroadduct to vacuum, followed by an inertatmosphere such as nitrogen or argon, and optionally repeating thevacuum and inert gas cycle one or more times; or [2] while calcining thesmectite heteroadduct in a fluidizing gas of air or carbon monoxide,changing the fluidizing gas to an inert gas such as nitrogen or argon.

Aspect 76. A method of making a support-activator according to any oneof Aspects 5-75, wherein the concentration of the smectite heteroadductsolids in the slurry is at least about 5 wt. %.

Aspect 77. A method of making a support-activator according to any oneof Aspects 5-76, wherein the concentration of the smectite heteroadductsolids in the slurry is up to about 30 wt. %, up to about 25 wt. %, upto about 20 wt. %, up to about 15 wt. %, up to about 10 wt. %, up toabout 5 wt. %, or wherein the concentration of the smectite heteroadductsolids in the slurry is in a range of from about 2 wt. % to about 30 wt.%, from about 3 wt. % to about 20 wt. %, or from about 5 wt. % to about15 wt. %.

Aspect 78. A method of making a support-activator according to any oneof Aspects 5-77, wherein the contacting step is conducted in thesubstantial absence of an ion-exchanged clay, a protic-acid-treatedclay, an aluminoxane, a borate co-activator, or any combination thereof.

Aspect 79. A method of making a support-activator according to any oneof Aspects 5-78, wherein the contacting step is conducted within atemperature range of from about 20° C. to about 100° C.

Aspect 80. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-79, wherein the slurry of the smectiteheteroadduct is characterized by the following filtration behavior:

[a] when the heteroadduct slurry, having a heteroadduct concentration of2.0 wt. % in water, is filtered within a time period of 0 hours to 2hours after the contacting step b), the proportion of a filtrateobtained at a filtration time of 10 minutes using either vacuumfiltration or gravity filtration, based upon the weight of the liquidcarrier in the slurry of the smectite heteroadduct is in a range of (1)from about 50% to about 100% by weight of the liquid carrier in theslurry before filtration, (2) from about 60% to about 100% by weight ofthe liquid carrier in the slurry before filtration, (3) from about 70%to about 100% by weight of the liquid carrier in the slurry beforefiltration, or (4) from about 80% to about 100% by weight of the liquidcarrier in the slurry before filtration; and

[b] the filtrate from the heteroadduct slurry, when evaporated, yieldssolids comprising less than 20%, less than 15%, or less than 10% of theinitial combined weight of clay and heterocoagulation agent.

Aspect 81. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-79, wherein the slurry of the smectiteheteroadduct is characterized by the following filtration behavior:

[a] when the heteroadduct slurry, having a heteroadduct concentration of2.0 wt. % in water, is filtered within a time period of 0 hours to 2hours after the contacting step b) to provide a first filtrate, theweight ratio of a second filtrate to the first filtrate is less than0.25, less than 0.20, less than 0.10, less than 0.15, less than 0.10,less than 0.5, or about 0.0, wherein the second filtrate is obtainedfrom filtration of a 2.0 wt. % slurry of a pillared clay prepared usingthe colloidal smectite clay, the heterocoagulation reagent, and theliquid carrier, and wherein the weight of the first filtrate and theweight of the second filtrate are measured after identical filtrationtimes of 5 minutes, 10 minutes or 15 minutes; and

[b] the filtrate from the heteroadduct slurry, when evaporated, yieldssolids comprising less than 20%, less than 15%, or less than 10% of theinitial combined weight of clay and heterocoagulation agent.

Aspect 82. A support-activator or a method of making a support-activatoraccording to any one of Aspects 4-79, wherein the slurry of the smectiteheteroadduct is characterized by a settling rate of a 2.5 wt. %composition of an aqueous heteroadduct slurry that is 3 times, 3.5times, 4 times, 4.5 times, 5 times, 6 times, 7 times, 8 times, 9 times,or 10 times greater than the settling rate of a 2.5 wt. % of the aqueouspillared clay slurry prepared using the colloidal smectite clay, theheterocoagulation reagent, and the liquid carrier, wherein the settlingrates are compared at about 12 hours, about 18 hours, about 24 hours,about 30 hours, about 36 hours, about 48 hours, about 72 hours, about 95hours, about 96 hours, or about 100 hours, or more from the start of thesettling test.

Aspect 83. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3 and 6-68, wherein the metallocene compound isselected from at least one metallocene compound having olefinpolymerization activity when activated by an ion-exchanged clay, aprotic-acid-treated clay, a pillared clay, an aluminoxane, a borateco-activator, or any combination thereof.

Aspect 84. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, and 83 wherein the metallocene compoundcomprises, consists of, consists essentially of, or is selected from anon-bridged (non-ansa) metallocene compound or a bridged (ansa)metallocene compound.

Aspect 85. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 1-3, 6-68, and 83 wherein the metallocene compoundcomprises, consists of, consists essentially of, or is selected from acompound or a combination of compounds, each independently having theformula:

(X¹)(X²)(X³)(X⁴)M, wherein

a) M is selected from titanium, zirconium, or hafnium;

b) X¹ is selected from a substituted or an unsubstitutedcyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl,boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, wherein anysubstituent is selected independently from a halide, a C₁-C₂₀hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, a C₁-C₂₀ organoheteryl, a fusedC₄-C₁₂ carbocyclic moiety, or a fused C₄-C₁₁ heterocyclic moiety havingat least one heteroatom selected independently from nitrogen, oxygen,sulfur, or phosphorus;

c) X² is selected from: [1] a substituted or an unsubstitutedcyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, wherein anysubstituent is selected independently from a halide, a C₁-C₂₀hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀ organoheteryl; or[2] a halide, a hydride, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀heterohydrocarbyl, a C₁-C₂₀ organoheteryl, a fused C₄-C₁₂ carbocyclicmoiety, or a fused C₄-C₁₁ heterocyclic moiety having at least oneheteroatom selected independently from nitrogen, oxygen, sulfur, orphosphorus;

d) wherein X¹ and X² are optionally bridged by at least one linkersubstituent having from 2 to 4 bridging atoms selected independentlyfrom C, Si, N, P, or B, wherein each available non-bridging valence ofeach bridging atom is unsubstituted (bonded to H) or substituted,wherein any substituent is selected independently from, a halide, aC₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀organoheteryl, and wherein any hydrocarbyl, heterohydrocarbyl, ororganoheteryl substituent can form a saturated or unsaturated cyclicstructure with a bridging atom or with X¹ or X²;

e) [1] X³ and X⁴ are selected independently from a halide, a hydride, aC₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀organoheteryl; [2] [GX^(A) _(k)X^(B) _(4-k)]⁻, wherein G is B or Al, kis a number from 1 to 4, and X^(A) in each occurrence is selectedindependently from H or a halide, and X^(B) in each occurrence isselected independently from a C₁-C₁₂ hydrocarbyl, a C₁-C₁₂heterohydrocarbyl, a C₁-C₁₂ organoheteryl; [3] X³ and X⁴ together are aC₄-C₂₀ polyene; or [4] X³ and X⁴ together with M form a substituted oran unsubstituted, saturated or unsaturated C₃-C6 metallacycle moiety,wherein any substituent on the metallacycle moiety is selectedindependently from a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀heterohydrocarbyl, or a C₁-C₂₀ organoheteryl.

Aspect 86. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toAspect 85, wherein X¹ and X² are bridged by a linker substituentselected from:

a) >EX⁵ ₂, -EX⁵ ₂EX⁵ ₂—, -EX⁵ ₂EX⁵EX⁵ ₂—, or >C═CX⁵ ₂, wherein E in eachoccurrence is independently selected from C or Si;

b) —BX⁵—, —NX⁵—, or —PX⁵—; or

c) [—SiX⁵ ₂(1,2-C₆H₄)SiX⁵ ₂—], [—CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂—], [—SiX⁵₂(1,2-C₆H₄)CX⁵ ₂—], [—SiX⁵ ₂(1,2-C₂H₂)SiX⁵ ₂—], [—CX⁵ ₂(1,2-C₆H₄)CX⁵₂-], or [—SiX⁵ ₂(1,2-C₆H₄)CX⁵ ₂—];

wherein X⁵ in each occurrence is selected independently from H, ahalide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a C₁-C₂₀organoheteryl;

and wherein any X⁵ substituents selected from hydrocarbyl,heterohydrocarbyl, or organoheteryl substituent can form a saturated orunsaturated cyclic structure with a bridging atom, another X⁵substituent, X¹, or X².

Aspect 87. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toAspect 85, wherein X¹ and X² are bridged by a linker substituentselected from a C₁-C₂₀ hydrocarbylene group, a C₁-C₂₀ hydrocarbylidenegroup, a C₁-C₂₀ heterohydrocarbyl group, a C₁-C₂₀ heterohydrocarbylidenegroup, a C₁-C₂₀ heterohydrocarbylene group, or a C₁-C₂₀heterohydrocarbylidene group.

Aspect 88. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toAspect 85, wherein X¹ and X² are bridged by at least one substituenthaving the formula >EX⁵ ₂, -EX⁵ ₂EX⁵ ₂—, or —BX⁵—, wherein E isindependently C or Si, X⁵ in each occurrence is selected independentlyfrom a halide, a C₁-C₂₀ aliphatic group, a C₆-C₂₀ aromatic group, aC₁-C₂₀ heteroaliphatic group, a C₄-C₂₀ heteroaromatic group, or a C₁-C₂₀organoheteryl group.

Aspect 89. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 86-88, wherein X⁵ in each occurrence is selectedindependently from a halide, a C₁-C₁₈ or C₁-C₁₂ alkyl group, a C₂-C₁₈ orC₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂ aromatic group, a C₄-C₁₈ orC₄-C₁₂ heteroaromatic group, a C₁-C₁₈ or C₁-C₁₂ heterohydrocarbyl group,a C₁-C₂₁ or C₁-C₁₅ organosilyl group, a C₁-C₁₈ or C₁-C₁₂ alkyl halide(haloalkyl) group, a C₁-C₁₈ or C₁-C₁₂ organophosphorus group, or aC₁-C₁₈ or C₁-C₁₂ organonitrogen group.

Aspect 90. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toAspect 85, wherein X¹ and X² are bridged by a linker substituentselected from silylene, methylsilylene, dimethylsilylene,diisopropylsilylene, dibutylsilylene, methylbutylsilylene,methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene,methylphenylsilylene, diphenylsilylene, ditolylsilylene,methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene,cyclotrimethylenesilylene, cyclotetramethylenesilylene,cyclopentamethylenesilylene, cyclohexamethylenesilylene, orcycloheptamethylenesilylene.

Aspect 91. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-90, wherein X¹ is selected from a substituted oran unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein anysubstituent is selected independently from a halide, a C₁-C₂₀ aliphaticgroup, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphatic group, a C₄-C₂₀heteroaromatic group, or a C₁-C₂₀ organoheteryl group.

Aspect 92. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-90, wherein X¹ is selected from a substituted oran unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein anysubstituent is selected independently from a halide, a C₁-C₁₈ or C₁-C₁₂alkyl group, a C₂-C₁₈ or C₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂aromatic group, a C₄-C₁₈ or C₄-C₁₂ heteroaromatic group, a C₁-C₂₁ orC₁-C₁₅ organosilyl group, a C₁-C₁₈ or C₁-C₁₂ alkyl halide (haloalkyl)group, a C₁-C₁₈ or C₁-C₁₂ organophosphorus group, or a C₁-C₁₈ or C₁-C₁₂organonitrogen group.

Aspect 93. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-90, wherein X¹, X², or both X¹ and X² are selectedindependently from a substituted or an unsubstituted cyclopentadienyl,indenyl, or fluorenyl, wherein any substituent is selected independentlyfrom:

a) a silicon group having the formula —SiH₃, —SiH₂R, —SiHR₂, —SiR₃,—SiR₂(OR), —SiR(OR)₂, or —Si(OR)₃;

b) a phosphorus group having the formula —PHR, —PR₂, —P(O)R₂, —P(OR)₂,—P(O)(OR)₂, —P(NR₂)₂, or —P(O)(NR₂)₂;

c) a boron group having the formula —BH₂, —BHR, —BR₂, —BR(OR), or—B(OR)₂;

d) a germanium group having the formula —GeH₃, —GeH₂R, —GeHR₂, —GeR₃,—GeR₂(OR), —GeR(OR)₂, or —Ge(OR)₃; or

e) any combination thereof;

wherein R in each occurrence is selected independently from a C₁-C₂₀hydrocarbyl group.

Aspect 94. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-90, wherein X¹, X², or X¹ and X² are substitutedwith a fused carbocyclic or heterocyclic moiety selected from pyrrole,furan, thiophene, phosphole, imidazole, imidazoline, pyrazole,pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, thiazole,thiazoline, isothiozoline, or a partially saturated analogs thereof.

Aspect 95. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-92, wherein X² is selected from: [1] a substitutedor an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein anysubstituent is selected independently from a halide, a C₁-C₂₀ aliphaticgroup, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphatic group, a C₄-C₂₀heteroaromatic group, or a C₁-C₂₀ organoheteryl group; or [2] a halide,a C₁-C₂₀ aliphatic group, a C₆-C₂₀ aromatic group, a C₁-C₂₀heteroaliphatic group, a C₄-C₂₀ heteroaromatic group, or a C₁-C₂₀organoheteryl group.

Aspect 96. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-92, wherein X² is selected from: [1] a substitutedor an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein anysubstituent is selected independently from a halide, a C₁-C₁₈ or C₁-C₁₂alkyl group, a C₂-C₁₈ or C₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂aromatic group, a C₄-C₁₈ or C₄-C₁₂ heteroaromatic group, a C₁-C₂₁ orC₁-C₁₅ organosilyl group, a C₁-C₁₈ or C₁-C₁₂ alkyl halide (haloalkyl)group, a C₁-C₁₈ or C₁-C₁₂ organophosphorus group, or a C₁-C₁₈ or C₁-C₁₂organonitrogen group; or [2] a halide, a C₁-C₁₈ or C₁-C₁₂ alkyl group, aC₂-C₁₈ or C₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂ aromatic group, aC₄-C₁₈ or C₄-C₁₂ heteroaromatic group, a C₁-C₂₁ or C₁-C₁₅ organosilylgroup, a C₁-C₁₈ or C₁-C₁₂ alkyl halide (haloalkyl) group, a C₁-C₁₈ orC₁-C₁₂ organophosphorus group, or a C₁-C₁₈ or C₁-C₁₂ organonitrogengroup.

Aspect 97. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-96, wherein at least one of X¹, X², or the linkingsubstituent between X¹ and X² is substituted with a C₃-C₁₂ olefinicgroup having the formula —(CH₂)_(n)CH═CH₂, wherein n is from 1-10.

Aspect 98. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-97, wherein: [1] X³ and X⁴ are selectedindependently from a halide, a hydride, a C₁-C₂₀ aliphatic group, aC₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphatic group, a C₄-C₂₀heteroaromatic group, or a C₁-C₂₀ organoheteryl group; [2] X³ and X⁴together are a substituted or an unsubstituted 1,3-butadiene having from4 to 20 carbon atoms; or [3] X³ and X⁴ together with M form asubstituted or an unsubstituted, saturated or unsaturated C₄-C₅metallacycle moiety, wherein any substituent on the metallacycle moietyis selected independently from a halide, a C₁-C₂₀ aliphatic group, aC₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphatic group, a C₄-C₂₀heteroaromatic group, or a C₁-C₂₀ organoheteryl group.

Aspect 99. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-97, wherein: [1] X³ and X⁴ are selectedindependently from a halide, a hydride, a C₁-C₁₈ or C₁-C₁₂ alkyl group,a C₂-C₁₈ or C₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂ aromatic group, aC₄-C₁₈ or C₄-C₁₂ heteroaromatic group, a C₁-C₂₁ or C₁-C₁₅ organosilylgroup, a C₁-C₁₈ or C₁-C₁₂ alkyl halide (haloalkyl) group, a C₁-C₁₈ orC₁-C₁₂ organophosphorus group, or a C₁-C₁₈ or C₁-C₁₂ organonitrogengroup; or [2] X³ and X⁴ together are a substituted or an unsubstituted1,3-butadiene having from 4 to 18 carbon atoms; or [3] X³ and X⁴together with M form a substituted or an unsubstituted, saturated orunsaturated C₄-C₅ metallacycle moiety, wherein any substituent on themetallacycle moiety is selected independently from a halide, a C₁-C₁₈ orC₁-C₁₂ alkyl group, a C₂-C₁₈ or C₂-C₁₂ alkenyl group, a C₆-C₁₈ or C₆-C₁₂aromatic group, a C₄-C₁₈ or C₄-C₁₂ heteroaromatic group, a C₁-C₂₁ orC₁-C₁₅ organosilyl group, a C₁-C₁₈ or C₁-C₁₂ alkyl halide (haloalkyl)group, a C₁-C₁₈ or C₁-C₁₂ organophosphorus group, or a C₁-C₁₈ or C₁-C₁₂organonitrogen group.

Aspect 100. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 85-97, wherein X³ and X⁴ are selected independentlyfrom [1] a halide, a hydride, a borohydride, an aluminum hydride; or [2]a substituted or an unsubstituted C₁-C₁₈ aliphatic group, C₁-C₁₂alkoxide group, C₆-C₁₀ aryloxide group, C₁-C₁₂ alkylsulfide group,C₆-C₁₀ arylsulfide group, wherein any substituent is selectedindependently from a halide, a C₁-C₁₀ alkyl, or a C₆-C₁₀ aryl; or [3] anamido group or a phosphido group, wherein any substituent is selectedindependently from a C₁-C₁₀ alkyl or a C₆-C₁₀ aryl.

Aspect 101. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst, according toany one of Aspects 1-3, 6-68, or 83, wherein the metallocene compoundcomprises, consists of, consists essentially of, or is selected frombis(cyclopentadienyl)zirconium dichloride,bis-(methylcyclopentadienyl)zirconium dichloride,bis(1,2-dimethylcyclopentadienyl)zirconium dichloride,bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride,bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride,bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,bis-(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride,bis-(ethylcyclopentadienyl)zirconium dichloride,bis(1,2-diethylcyclopentadienyl)zirconium dichloride,bis(1,3-diethylcyclopentadienyl)zirconium dichloride,bis(isopropylcyclopentadienyl)zirconium dichloride,bis(phenylpropylcyclopentadienyl)zirconium dichloride,bis(t-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)-zirconiumdichloride, bis(4-methyl-1-indenyl)zirconium dichloride,bis(5-methyl-1-indenyl)zirconium)zirconium dichloride,bis(6-methyl-1-indenyl)zirconium dichloride,bis(7-methyl-1-indenyl)zirconium dichloride,bis(5-methoxy-1-indenyl)-zirconium dichloride,bis(2,3-dimethyl-1-indenyl)zirconium dichloride,bis(4,7-dimethyl-1-indenyl)zirconium dichloride,bis(4,7-dimethoxy-1-indenyl)zirconium dichloride,(indenyl)(fluorenyl)zirconium dichloride, bis(fluorenyl)zirconiumdichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride,bis(trimethylgermylcyclopentadienyl)zirconium dichloride,bis(trimethylstanylcyclopentadienyl)zirconium dichloride,bis(trifluoromethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)-(methylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(dimethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(trimethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(ethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(diethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(triethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(tetraethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(pentaethylcyclopentadienyl)-zirconium dichloride,(cyclopentadienyl)(fluorenyl)zirconium dichloride,(cyclopentadienyl)(2,7-di-t-butylfluorenyl)-zirconium dichloride,(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(cyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,(methylcyclopentadienyl)-(t-butylcyclopentadienyl)zirconium dichloride,(methylcyclopentadienyl)(fluorenyl)zirconium dichloride,(methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(methylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(methylcyclopentadienyl)(4-methoxyfluorenyl)-zirconium dichloride,(dimethylcyclopentadienyl)(fluorenyl)-zirconium dichloride,(dimethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(dimethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(dimethylcyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(fluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,(diethylcyclopentadienyl)-(fluorenyl)zirconium dichloride,(diethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(diethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(diethylcyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride, orany combination thereof.

Aspect 102. A catalyst composition or a process for polymerizing olefinsaccording to any one of Aspects 1-3, 6-68, or 83-101, wherein thecatalyst composition further comprises a co-catalyst.

Aspect 103. A method of making an olefin polymerization catalystaccording to any one of Aspects 1-3, 6-68, or 83-102, wherein thecontacting step further comprises contacting, in any order, themetallocene compound and the support-activator with a co-catalyst.

Aspect 104. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-103, wherein the co-catalyst comprisesan alkylating agent, a hydriding agent, or a silylating agent.

Aspect 105. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from anorganoaluminum compound, an organoboron compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof.

Aspect 106. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from anorganoaluminum compound or a combination of organoaluminum compounds,each independently having the formula:

Al(X^(A))_(n)(X^(B))_(m) or M^(x)[AlX^(A) ₄], wherein

a) n+m=3, wherein n and m are not limited to integers;

b) X^(A) is selected independently from: [1] a hydride, a C₁-C₂₀hydrocarbyl, or a C₁-C₂₀ heterohydrocarbyl; [2] a hydride, a C₁-C₂₀aliphatic group, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphaticgroup, or a C₄-C₂₀ heteroaromatic group; or [3] two X^(A) togethercomprise a C₄-C₅ hydrocarbylene group and the remaining X^(A) is/areselected independently from a hydride, a C₁-C₂₀ hydrocarbyl, or a C₁-C₂₀heterohydrocarbyl;

c) X^(B) is selected independently from: [1] a halide or a C₁-C₂₀organoheteryl; or [2] a halide, a C₁-C₁₂ alkoxide group, or a C₆-C₁₀aryloxide group; and

d) M^(x) is selected from Li, Na, or K.

Aspect 107. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 102-103, wherein the co-catalyst comprises, consists of,consists essentially of, or is selected from an organoaluminum compoundor a combination of organoaluminum compounds, each independently havingthe formula:

Al(X^(C))_(n)(X^(D))_(3-n) or M^(x)[AlX^(C) ₄], wherein

a) n is a number from 1 to 3, inclusive;

b) X^(C) is selected independently from a hydride or a C₁-C₂₀hydrocarbyl;

c) X^(D) is a formal anionic species selected independently from:fluoride; chloride; bromide; iodide; bromate; chlorate; perchlorate;hydrocarbylsulfate; hydrocarbylsulfite; sulfamate; hydrocarbylsulfide,hydrocarbylcarbonate; hydrogen-carbonate (bicarbonate); carbamate;nitrite; nitrate; hydrocarbyloxalate; dihydrocarbylphosphate;hydrocarbylselenite; sulfate; sulfite; carbonate; oxalate; phosphate;phosphite; selenite; selenide; sulfide; oxide; sulfamate; azide;alkoxide; amido; hydrocarbylamido; dihydrocarbylamido;R^(A)[CON(R)]_(q); wherein R^(A) in each occurrence is independently Hor a substituted or unsubstituted C₁-C₂₀ hydrocarbyl group and q is aninteger from 1 to 4, inclusive; and R^(B)[CO₂]_(r), wherein R^(B) ineach occurrence is independently H or a substituted or unsubstitutedC₁-C₂₀ hydrocarbyl group and r is an integer from 1 to 3, inclusive; and

d) M^(x) is selected from Li, Na, or K.

Aspect 108. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from: [1]trimethylaluminum, triethylaluminum (TEA), tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum,ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide,diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminumchloride, or any combination or mixture thereof; or [2]ethyl-(3-alkylcyclopentadiyl)aluminum, triisobutylaluminum (TIBAL),trioctylaluminum, or any combination or mixture thereof; or [3] anycombination of mixture of any one or more co-catalyst [1] and any one ormore co-catalyst [2].

Aspect 109. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst orco-activator comprises, consists of, consists essentially of, or isselected from an organoboron compound or a combination of organoboroncompounds, each independently having the formula:

B(X^(E))_(q)(X^(F))_(3-q), B(X^(E))₃, or M^(y)[BX^(E) ₄], wherein

a) q is from 1 to 3, inclusive;

b) X^(E) is selected independently from: [1] a hydride, a C₁-C₂₀hydrocarbyl, or a C₁-C₂₀ heterohydrocarbyl; [2] a hydride, a C₁-C₂₀aliphatic group, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphaticgroup, or a C₄-C₂₀ heteroaromatic group; [3] a fluorinated C₁-C₂₀hydrocarbyl, or a fluorinated C₁-C₂₀ heterohydrocarbyl; or [4] afluorinated C₁-C₂₀ aliphatic group, a fluorinated C₆-C₂₀ aromatic group,a fluorinated C₁-C₂₀ heteroaliphatic group, or a fluorinated C₄-C₂₀heteroaromatic group;

c) X^(F) is selected independently from: [1] a halide or a C₁-C₂₀organoheteryl; or [2] a halide, a C₁-C₁₂ alkoxide group, or a C₆-C₁₀aryloxide group; and

d) M^(y) is selected from Li, Na, or K.

Aspect 110. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst orco-activator comprises, consists of, consists essentially of, or isselected from [1] trimethylboron, triethylboron, tripropylboron,tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide,diisobutylboron hydride, triisobutylboron, diethylboron chloride,di-3-pinanylborane, pinacolborane, catecholborane, lithium borohydride,lithium triethylborohydride, a Lewis base adduct thereof, or anycombination or mixture thereof; or [2] tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination ormixture thereof.

Aspect 111. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from an organozincor organomagnesium compound or a combination of organozinc and/ororganomagnesium compounds, each independently having the formula:

M^(C)(X^(G))_(r)(X^(H))_(2-r), wherein

a) M^(C) is zinc or magnesium;

a) r is a number from 1 to 2, inclusive;

b) X^(G) is selected independently from: [1] a hydride, a C₁-C₂₀hydrocarbyl, or a C₁-C₂₀ heterohydrocarbyl; or [2] a hydride, a C₁-C₂₀aliphatic group, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphaticgroup, or a C₄-C₂₀ heteroaromatic group; and

c) X^(H) is selected independently from: [1] a halide or a C₁-C₂₀organoheteryl; or [2] a halide, a C₁-C₁₂ alkoxide group, or a C₆-C₁₀aryloxide group.

Aspect 112. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from: [1]dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc,diphenylzinc, or any combination thereof; [2] butylethylmagnesium,dibutylmagnesium, n-butyl-sec-butylmagnesium,dicyclopentadienylmagnesium, or any combination thereof; or [3] anycombination of any organozinc co-catalyst from group [1] and anyorganomagnesium co-catalyst from group [2].

Aspect 113. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from anorganolithium compound having the formula:

Li(X^(J)), wherein

X^(J) is selected independently from: [1] a hydride, a C₁-C₂₀hydrocarbyl, or a C₁-C₂₀ heterohydrocarbyl; or [2] a hydride, a C₁-C₂₀aliphatic group, a C₆-C₂₀ aromatic group, a C₁-C₂₀ heteroaliphaticgroup, or a C₄-C₂₀ heteroaromatic group.

Aspect 114. A catalyst composition, a process for polymerizing olefins,a method of making an olefin polymerization catalyst, according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the co-catalyst comprises,consists of, consists essentially of, or is selected from methyllithium,ethyllithium, propyllithium, butyllithium (including n-butyllithium andt-butyllithium), hexyllithium, iso-butyllithium, or any combinationthereof.

Aspect 115. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the catalyst compositionfurther comprises a co-activator selected from an ion-exchanged clay, aprotic-acid-treated clay, a pillared clay, an aluminoxane, a borateco-activator, an aluminate co-activator, an ionizing ionic compound, asolid oxide treated with an electron withdrawing anion, or anycombination thereof.

Aspect 116. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein the catalyst compositionfurther comprises an ionic ionizing compound.

Aspect 117. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 116, wherein the ionic ionizing compound comprises, consists of,consists essentially of, or is selected from tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronapthyl)borate, triethylammoniumtetrakis(perfluoronapthyl)borate, tripropylammoniumtetrakis(perfluoronapthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronapthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronapthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronapthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronapthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronapthyl)borate, tropilliumtetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluoronapthyl)borate, triphenylphosphoniumtetrakis(perfluoronapthyl)borate, triethylsilyliumtetrakis(perfluoronapthyl)borate, benzene(diazonium)tetrakis(perfluoronapthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,and dicyclohexylammonium tetrakis(pentafluorophenyl)borate; andadditional tri-substituted phosphonium salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, orany combination thereof.

Aspect 118. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-104, wherein catalyst compositionfurther comprises a co-activator comprising a solid oxide treated withan electron withdrawing anion.

Aspect 119. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 118, wherein:

a) the solid oxide comprises, consists of, consists essentially of, oris selected from silica, alumina, silica-alumina, silica-coated alumina,silica-zirconia, silica-titania, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or any combination thereof; and

b) the electron-withdrawing anion comprises, consists of, consistsessentially of, or is selected from fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate, or any combination thereof.

Aspect 120. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 118, wherein the co-activator comprises, consists of, consistsessentially of, or is selected from fluorided alumina, chloridedalumina, bromided alumina, sulfated alumina, fluorided silica-alumina,chlorided silica-alumina, bromided silica-alumina, sulfatedsilica-alumina, fluorided silica-zirconia, chlorided silica-zirconia,bromided silica-zirconia, sulfated silica-zirconia, fluoridedsilica-titania, or any combinations thereof.

Aspect 121. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-120, wherein the catalyst compositionfurther comprises a carrier or diluent, or the contacting in any orderoccurs in a carrier or diluent.

Aspect 122. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 121, wherein the carrier or diluent comprises, consists of,consists essentially of, or is selected from a hydrocarbon, an ether, ora combination thereof, each of which has from 1 to 20 carbon atoms.

Aspect 123. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 121, wherein the carrier or diluent comprises, consists of,consists essentially of, or is selected from cyclohexane, isobutane,n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, Isopar™,at least one olefin, or any combination thereof.

Aspect 124. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according toAspect 121, wherein the carrier or diluent comprises, consists of,consists essentially of, or is selected from at least one olefin.

Aspect 125. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-124, wherein the activity of a catalystis greater than or equal to about 300 grams of polyolefin per gram ofthe support-activator comprising a calcined smectite heteroadduct perhour (g/g/hr), under polymerization conditions comprising [1] ametallocene compound to calcined smectite heteroadduct ratio of about7×10⁻⁵ mmol metallocene compound/mg calcined smectite heteroadduct, and[2] other standard conditions as described in the specification.

Aspect 126. A catalyst composition, a process for polymerizing olefins,or a method of making an olefin polymerization catalyst according to anyone of Aspects 1-3, 6-68, or 83-125, wherein the catalyst compositioncomprises the organoaluminum compound and the calcined smectiteheteroadduct in a relative concentration expressed in moles oforganoaluminum compound per gram of calcined smectite heteroadduct in arange of from about 0.5 to about 0.000005, from about 0.1 to about0.00001, or from about 0.01 to about 0.0001.

Aspect 127. A process for polymerizing olefins according to any one ofAspects 1-3, 6-68, or 83-126, wherein the process comprises at least oneslurry polymerization, at least one gas phase polymerization, at leastone solution polymerization, or any multi-reactor combinations thereof.

Aspect 128. A process for polymerizing olefins according to any one ofAspects 1-3, 6-68, or 83-127, wherein the process comprisespolymerization in a gas phase reactor, a slurry loop, dual slurry loopsin series, multiple slurry tanks in series, a slurry loop combined witha gas phase reactor, a continuous stirred reactor in a batch process, orcombinations thereof.

Aspect 129. A process for polymerizing olefins according to any one ofAspects 1-3, 6-68, or 83-128, wherein the polyolefin comprises, consistsof, consists essentially of, or is selected from an olefin homopolymeror an olefin copolymer.

Aspect 130. A process for polymerizing olefins according to any one ofAspects 1-3, 6-68, or 83-129, wherein the polyolefin comprises, consistsof, consists essentially of, or is selected from an olefin homopolymer,the homopolymer comprising olefin monomer residues having from 2 toabout 20 carbon atoms per monomer molecule.

Aspect 131. A process for polymerizing olefins according to Aspect 130,wherein the olefin monomer is selected from ethylene, propylene,1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, or 1-decene.

Aspect 132. A process for polymerizing olefins according to any one ofAspects 2, 6-68, or 83-129, wherein the polyolefin comprises, consistsof, consists essentially of, or is selected from an ethylene-olefincomonomer copolymer, the copolymer comprising α-olefin comonomerresidues having from 3 to about 20 carbon atoms per monomer molecule.

Aspect 133. A process for polymerizing olefins according to Aspect 132,wherein the olefin comonomer is selected from an aliphatic C₃ to C₂₀olefin, a conjugated or nonconjugated C₃ to C₂₀ diolefin, or any mixturethereof.

Aspect 134. A process for polymerizing olefins according to Aspect 132,wherein the olefin comonomer is selected from propylene, 1-butene,2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1,3-butadiene, isoprene, piperylene,2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene,vinylcyclohexane, or any combination thereof.

Aspect 135. A method of making an olefin polymerization catalystaccording to any one of Aspects 3, 6-68, or 83-126, wherein:

a) the metallocene compound and the co-catalyst are contacted [1] for atime period from about 1 minute to about 24 hours or from about 1 minuteto about 1 hour and [2] at a temperature from about 10° C. to about 200°C. or from about 15° C. to about 80° C., to form a first mixture;followed by

b) contacting the first mixture with the support-activator comprising acalcined smectite heteroadduct to form the catalyst composition.

Aspect 136. A method of making an olefin polymerization catalystaccording to any one of Aspects 3, 6-68, or 83-126, wherein themetallocene compound, the co-catalyst, and the support-activatorcomprising a calcined smectite heteroadduct are contacted [1] for a timeperiod from about 1 minute to about 6 months or from about 1 minute toabout 1 week and [2] at a temperature from about 10° C. to about 200° C.or from about 15° C. to about 80° C., to form the olefin polymerizationcatalyst.

Aspect 137. A catalyst composition prepared according to any one ofAspects 3, 6-68, 83-126, or 135-136.

Aspect 138. A process for polymerizing olefins comprising contacting atleast one olefin monomer and a catalyst composition under polymerizationconditions to form a polyolefin, wherein the catalyst composition isprepared according to Aspect 137.

Aspect 139. A catalyst composition, a process for polymerizing olefins,a method of making an olefin polymerization catalyst, asupport-activator, or a method of making a support-activator accordingto any one of Aspects 1-138, wherein the catalyst composition,processes, methods, and support-activators are any catalyst composition,processes, methods, and support-activators disclosed herein.

We claim:
 1. A catalyst composition for olefin polymerization, thecatalyst composition comprising: (a) at least one support-activatorcomprising a calcined smectite heteroadduct, the smectite heteroadductcomprising the contact product in a liquid carrier of [1] a colloidalsmectite clay and [2] a heterocoagulation reagent comprising at leastone cationic polymetallate and in an amount sufficient to provide aslurry of the smectite heteroadduct having a zeta potential in a rangeof from about positive (+)25 mV (millivolts) to about negative (−)25 mV,as quantified from the Electrokinetic Sonic Amplitude (ESA) Effect; and(b) at least one metallocene compound having the formula(X¹)(X²)(X³)(X⁴)M, wherein: (i) M is zirconium or hafnium; (ii) X¹ is asubstituted or unsubstituted indenyl, fluorenyl, or cyclopentadienylwherein any substituent is selected independently from a C₁-C₂₀hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a fused C₄-C₁₂ carbocyclicmoiety; (iii) X² is a substituted or unsubstituted indenyl orcyclopentadienyl, wherein any substituent is selected independently froma C₁-C₂₀ hydrocarbyl or a C₁-C₂₀ heterohydrocarbyl; (iv) X³ and X⁴ areselected independently from a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀heterohydrocarbyl, or a C₁-C₂₀ organoheteryl; and (v) X¹ and X² areoptionally bridged by a linking substituent >EX⁵ ₂, wherein E isselected from C or Si, and each X⁵ is selected independently from aC₁-C₂₀ hydrocarbyl.
 2. The catalyst composition according to claim 1,wherein: (a) X¹ and X² are independently a substituted or anunsubstituted indenyl; and (b) X¹ and X² are bridged by a linkersubstituent >EX⁵ ₂.
 3. The catalyst composition according to claim 1,wherein: (a) X¹ and X² are independently a substituted or anunsubstituted indenyl; and (b) X¹ and X² are unbridged.
 4. The catalystcomposition according to claim 1, wherein: (a) X¹ is a substituted or anunsubstituted fluorenyl; (b) X² is a substituted cyclopentadienyl; and(c) X¹ and X² are bridged by a linker substituent >EX⁵ ₂.
 5. Thecatalyst composition according to claim 1, wherein: (a) X¹ is asubstituted or an unsubstituted indenyl; (b) X² is a substituted or anunsubstituted cyclopentadienyl; and (c) X¹ and X² are bridged by alinker substituent >EX⁵ ₂.
 6. The catalyst composition according toclaim 1, wherein: (a) X¹ and X² are independently a substitutedcyclopentadienyl; and (b) X¹ and X² are unbridged.
 7. The catalystcomposition according to claim 1, wherein the linker substituent >EX⁵ ₂is present, and X⁵ in each occurrence is selected independently from aC₁-C₁₂ alkyl group, or C₂-C₁₂ alkenyl group, or a C₆-C₁₂ aromatic group.8. The catalyst composition according to claim 1, wherein anysubstituent on X¹ and X² is selected independently from a C₁-C₁₂ alkylgroup, a C₂-C₁₂ alkenyl group, a C₆-C₁₂ aromatic group, a C₄-C₁₂heteroaromatic group, or a C₁-C₁₅ organosilyl group.
 9. The catalystcomposition according to claim 1, wherein at least one of X¹, X², or theE atom of the linking substituent >EX⁵ ₂, when present, is substitutedwith a C₃-C₁₂ olefinic group having the formula —(CH₂)_(n)CH═CH₂,wherein n is from 1-10.
 10. The catalyst composition according to claim1, wherein the metallocene compound comprisesbis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride,bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride,bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,bis-(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride,bis(1,3-diethylcyclopentadienyl)-zirconium dichloride,bis(indenyl)zirconium dichloride, bis(4-methyl-1-indenyl)zirconiumdichloride, bis(5-methyl-1-indenyl)zirconium)zirconium dichloride,bis(6-methyl-1-indenyl)zirconium dichloride,bis(7-methyl-1-indenyl)zirconium dichloride,bis(5-methoxy-1-indenyl)-zirconium dichloride,bis(2,3-dimethyl-1-indenyl)zirconium dichloride,bis(4,7-dimethyl-1-indenyl)zirconium dichloride,bis(4,7-dimethoxy-1-indenyl)zirconium dichloride,(indenyl)(fluorenyl)zirconium dichloride,bis(trimethylsilylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(dimethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(trimethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(ethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(diethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(triethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(tetraethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(pentaethylcyclopentadienyl)-zirconium dichloride,(cyclopentadienyl)(2,7-di-t-butylfluorenyl)-zirconium dichloride,(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(methylcyclopentadienyl)-(t-butylcyclopentadienyl)zirconium dichloride,(methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(methylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(dimethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(dimethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(ethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,(diethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,(diethylcyclopentadienyl)(octahydrofluorenyl)-zirconium dichloride,bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride,rac-dimethylsilylene bis(2-methyl-4-phenylindenyl)zirconium dichloride,or any combination thereof.
 11. The catalyst composition according toclaim 1, wherein the catalyst composition further comprises: (c) atleast one co-catalyst comprising an alkylating agent, a hydriding agent,or a silylating agent.
 12. The catalyst composition according to claim11, wherein the co-catalyst comprises trimethylaluminum,triethylaluminum (TEA), tripropylaluminum, tributylaluminum,trihexylaluminum, trioctylaluminum,ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide,diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminumchloride, ethyl-(3-alkylcyclopentadiyl)aluminum, or any combinationthereof.
 13. The catalyst composition according to claim 1, wherein: thesmectite clay comprises montmorillonite, sauconite, nontronite,hectorite, beidellite, saponite, bentonite, or any combination thereof,and the smectite clay is optionally monocation exchanged with at leastone of lithium, sodium, or potassium.
 14. The catalyst compositionaccording to claim 1, wherein the cationic polymetallate compriseslinear, cyclic or cluster aluminum compounds containing from 2-30aluminum atoms.
 15. The catalyst composition according to claim 1,wherein the cationic polymetallate comprises polyaluminum chloride,aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminumoxyhydroxychloride.
 16. The catalyst composition according to claim 15,wherein the ratio of millimoles (mmol) of aluminum (Al) in thepolyaluminum chloride, aluminum chlorhydrate, aluminumsesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) ofcolloidal smectite clay is in a range of from about 0.2 mmol Al/g clayto about 2.5 mmol Al/g clay.
 17. The catalyst composition according toclaim 15, wherein the ratio of millimoles (mmol) of aluminum (Al) in thepolyaluminum chloride, aluminum chlorhydrate, aluminumsesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) ofcolloidal smectite clay is in a range of from about 0.5 mmol Al/g clayto about 2.2 mmol Al/g clay.
 18. The catalyst composition according toclaim 1, wherein the cationic polymetallate comprises a first metaloxide which is chemically-treated with a second metal oxide, a metalhalide, a metal oxyhalide, or a combination thereof, in an amountsufficient to provide a colloidal suspension of the chemically-treatedfirst metal oxide having a zeta potential of greater than positive 20 mV(millivolts).
 19. The catalyst composition according to claim 1, whereinthe cationic polymetallate comprises fumed silica, fumed alumina, fumedsilica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumedzirconia, fumed ceria, or any combination thereof, which ischemically-treated with polyaluminum chloride, aluminum chlorhydrate,aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or anycombination thereof.
 20. The catalyst composition according to claim 1,wherein the cationic polymetallate comprises aluminumchlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumedalumina, aluminum chlorhydrate-treated fumed silica-alumina, or anycombination thereof.
 21. The catalyst composition according to claim 1,wherein the liquid carrier comprises water.
 22. The catalyst compositionaccording to claim 21, wherein the liquid carrier further comprises asurfactant selected from an anionic surfactant, a cationic surfactant, anon-ionic surfactant, or an amphoteric surfactant.
 23. The catalystcomposition according to claim 22, wherein the cationic surfactant isselected from: a primary amine, a secondary amine, or a tertiary amine;or a primary ammonium chloride or bromide, a secondary ammonium chlorideor bromide, a tertiary ammonium chloride or bromide, or a quaternaryammonium chloride or bromide.
 24. The catalyst composition according toclaim 22, wherein the non-ionic surfactant is selected from anethoxylate, a glycol ether, a fatty alcohol polyglycol ether, or acombination thereof.
 25. The catalyst composition according to claim 1,wherein the colloidal smectite clay and the heterocoagulation reagentare contacted in an amount sufficient to provide a slurry of a smectiteheteroadduct having a zeta potential in a range of from about positive(+)20 mV (millivolts) to about negative (−)20 mV.
 26. The catalystcomposition according to claim 1, wherein the colloidal smectite clayand the heterocoagulation reagent are contacted in an amount sufficientto provide a slurry of a smectite heteroadduct having a zeta potentialin a range of from about positive (+)15 mV (millivolts) to aboutnegative (−)15 mV.
 27. A process for polymerizing olefins comprisingcontacting at least one olefin monomer and the catalyst compositionaccording to claim 1 under polymerization conditions to form apolyolefin.
 28. The process for polymerizing olefins according to claim27, wherein the at least one olefin monomer is selected from [a]ethylene or propylene, or [b] ethylene in combination with at least onecomonomer selected from propylene, 1-butene, 2-butene,3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1,3-butadiene, isoprene, piperylene,2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene,vinylcyclohexane, or any combination thereof.
 29. The process forpolymerizing olefins according to claim 27, wherein the processcomprises polymerization in a gas phase reactor, a slurry loop, dualslurry loops in series, multiple slurry tanks in series, a slurry loopcombined with a gas phase reactor, a continuous stirred reactor in abatch process, or combinations thereof.
 30. A method of making an olefinpolymerization catalyst composition, the method comprising contacting inany order: (a) at least one support-activator comprising a calcinedsmectite heteroadduct, the smectite heteroadduct comprising the contactproduct in a liquid carrier of [1] a colloidal smectite clay and [2] aheterocoagulation reagent comprising at least one cationic polymetallateand in an amount sufficient to provide a slurry of the smectiteheteroadduct having a zeta potential in a range of from about positive(+)25 mV (millivolts) to about negative (−)25 mV, as quantified from theElectrokinetic Sonic Amplitude (ESA) Effect; and (b) at least onemetallocene compound having the formula(X¹)(X²)(X³)(X⁴)M, wherein: (i) M is zirconium or hafnium; (ii) X¹ is asubstituted or unsubstituted indenyl, fluorenyl, or cyclopentadienylwherein any substituent is selected independently from a C₁-C₂₀hydrocarbyl, a C₁-C₂₀ heterohydrocarbyl, or a fused C₄-C₁₂ carbocyclicmoiety; (iii) X² is a substituted or unsubstituted indenyl orcyclopentadienyl, wherein any substituent is selected independently froma C₁-C₂₀ hydrocarbyl or a C₁-C₂₀ heterohydrocarbyl; (iv) X³ and X⁴ areselected independently from a halide, a C₁-C₂₀ hydrocarbyl, a C₁-C₂₀heterohydrocarbyl, or a C₁-C₂₀ organoheteryl; and (v) X¹ and X² areoptionally bridged by a linking substituent >EX⁵ ₂, wherein E isselected from C or Si, and each X⁵ is selected independently from aC₁-C₂₀ hydrocarbyl.
 31. The method of making an olefin polymerizationcatalyst composition according to claim 30, the method furthercomprising contacting in any order: (c) at least one co-catalystcomprising an alkylating agent, a hydriding agent, or a silylatingagent.